Preliminary Report For The Quantification Of Tetrachlorodibenzo-P-Dioxin Residues In Extracts Of Samples From A Municipal Incinerator


UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
date March 28, 1980
subject Preliminary Report for the Quantification of Tetrachlorodibenzo-p-diox1n
Residues In Extracts of Samples Collected From a Minicipal Incinerator
from Robert Harless
HERL, ETD, ACB (MD-69)
to Mr. J. B. Homolya, Chief
Gaseous Emissions Research Section
EMSL (MD-46)
THRU: Dr. R. G. Lewis, Chief	¦
Analytical Chemistry Branch
HERL, ETD, (MD-69)
The two sample extracts (RTP-118 and RTP-137) were received 3-18-80 from
Wright State University (WSU). An ACB Identification number (ACB-126)
was assigned to this project. These extracts represent the contents of
two traps from a stack gas sampling train which was used to sample the
effluents (gas phase) from a municipal incinerator that was burning
waste fuel. The samples were subjected to an extensive clean-up pro-
cedure by WSU and a portion of each extract was submitted to HERL* ACB
for collaborative analysis for TCDDs.
A Varlan NAT 311A mass spectrometer directly coupled to a 30 m x 0.25 ran
1.d. 0V-101 WCOT glass capillary column was utilized for these analyses.
The method of analysis Is described 1n the attached manuscript.
The criteria utilized for confirmation of 2,3,7,8-TCDD were:
1.	Correct capillary colunn 6C-HRMS retention time of 2,3,7,8-TCDD,
+ 15 seconds.
2.	Correct responses for the co-1nject1on of sample fortified with
37C1-TCDD and 2,3,7,8-TCDD.
3.	Molecular Ion chlorine Isotope ratio (m/z 320 and m/z 322).
4.	Capillary colunn GC-HRMS simultaneous multiple 1on monitoring
response for 37C1-TCDD and 2,3,7,8-TCDD (m/z 328, 322, and 320).
5.	M/z 320 and m/z 322 response greater than 2.5 irm noise level.
The capillary colunn GC-HRMS retention time of 2,3,7,8-TCDD was 20 minutes
+ 15 seconds. The MS mass resolution (9000) was sufficient to resolve
TCDDs from contamlnation. The masses monitored during these analyses were:
CPA ran U20-6 <*•». 3-76)

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1. m/z 318.9793 PFK reference
2.
m/z
319.8965 TCDD
3.
m/z
321.8935 TCDD
4.
m/z
327.8847 37C1U-TCDD
Results


The results shown 1n Table 1 mere reported to you on 3-19-80. The
recovery of 37Cli*-TCDD (sample preparation efficiency) was very good and
the extracts were very clean. A unique distribution of TCDD Isomers
(minimum of 6) Including 2,3,7,8-TCDD were resolved and detected In both
extracts. The Identification of the TCDD Isomers shown 1n Table 1 were
based on co-1nject1on of sample and the authentic TCDD Isomers available
1n this laboratory (1.2,3,4-, 2,3,6,8-, 2,3,7,8-TCDDs and a mixture of
702 1,3,6,8-TCDD and 30% of an unknown Isomer). Quantification of TCDD
Isomers was based on the HRMS sensitivity, peak height of m/z 320 and
m/z 322, for 10 pg 2,3,7,8-TCDD. The concentration of our solutions of
other TCDD Isomers has not been validated. A mlnlmun of three uniden-
tified TCDD Isomers were resolved and quantified.
Analyses for tetra through octa-TCDD will be performed on the small
nunber of sample extracts that will be submitted at a later date.
Specific samples will be subjected to analysis utilizing a polar cap-
illary column to provide more conclusive Identification of Isomers,
especially 2,3,7,8-TCDD.
Discussion of Results
1.	A m1n1mim of 6 TCDD isomers were detected in each extract.
2.	A TCDD Isomer that satisfies the analytical criteria for 2,3,7,8-
TCDD was detected 1n both samples. The concentration of this
isomer was minor compared to the total TCD0 concentration.
3.	The Isomer corresponding to 1,3,6,8-TCDD was present In the highest
concentration 1n both extracts.
4.	The distribution of TCDD Isomers was similar 1n both extracts. The
major difference was noted 1n the concentrations.
5.	It is emphasized that the Identification of Isomers was assigned
based on authentic standards but this does not necessarily mean
that they are correct. Other unavailable TCDD Isomers may have
exact retention times.

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6.	These analyses should be performed on a polar capillary column to
provide more conclusive confirmation of specific TCDD isomers.
7.	All TCDD isomers detected 1n these extracts, with the exception of
one very minor isomer, eluted before 2,3,7,8-TCDD. This fact sug-
gests that parent precursers were present in the fuel. This is not
the distribution of isomers that one would expect for the random
formation of TCDD from CI, etc., in a combustion process.
Sunmary
A minimum of six TCDD isomers including a small quantity of 2,3,7,8-TCDD
was detected In two extracts which represent the gas phase effluent of
a municipal incinerator.
CC: Mike Dellarco
Dr. D. E. Gardner
Dr. N. K. Wilson

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TABLE 1
PRELIMINARY RESULTS FOR TETRACHLORODIBENZO-P-DIOXIN RESIDUES IN SAMPLE
EXTRACTS WHICH REPRESENT THE GAS PHASE EFFLUENT OF A MUNICIPAL INCINERATOR
ID Number
37C1-TC0D
% Recovery
Total TCDD^
Detected (ng)
1,3,6,8-
TCDD (ng)
2,3,6,8-
TCDD (ng)
1.2,3,4-/
2,3,7,8-
TCDD (ng)
Unidentified
TCDD Isomers
(ng)
116
m
33.6
11.5
6.4
3.7/2.0
10
137
tz%
8.
2.7
1.7
0.5/0.5
2.6
^^Results are not corrected for recovery Tosses.

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