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United States
Environmental Protection
Agency
Air and Energy Engineering
Research Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S9-87/011 Aug. 1987
<>EPA Project Summary
PIC Analysis Methods
Ruby H. James, Linda B. Farr, Robert E. Adams, and Herbert C. Miller
Products of incomplete combustion
(PICs) may be formed during the in-
cineration of hazardous wastes. PiCs
may be defined as compounds in the
stack gas of an incinerator but not
present in the waste feed at a con-
centration of 100>g/g. In some
instances, the PICs formed may also be
constituents of the waste feed, thus
confusing the analysis of principal or-
ganic hazardous constituents (POHCs).
The total amount of hazardous PICs
can easily exceed the total of the original
POHCs chosen to monitor the trial burn.
The compounds may be identifiable as
fragments of incineration feed con-
stituents, products of complex recom-
binations, substitution reactions in the
flame or post-flame zone, or compounds
that enter the incineration process from
other sources.
Study efforts applied previously
developed POHC general analysis
methods to the analysis of PICs. A
large body of the literature on PICs is
based on the findings of polychlorinated
dibenzo-p-dioxins (PCDDs) and poly-
chlorinated dibenzofurans (PCDFs) in
incinerator effluents. Generalized GC/
FID and GC/MS analysis methods for
PCDDs and PCDFs were evaluated.
The generalized GC/FID and GC/MS
procedures were extended to many of
these compounds from a list of 121
compounds recently added to the
potential POHC list in Appendix VIII,
Part 261, 40 CFR.
This Project Summary was developed
by EPA's Air and Energy Engineering
Research Laboratory, Research Triangle
Park, NC, to announce key findings of
the research protect that Is fully docu-
mented In a separate report of the same
title (see Project Report ordering In-
formation at back).
Introduction
The EPA Methods Manual, "Sampling
and Analysis Methods for Hazardous
Waste Combustion," EPA-600/8-84-002
(NTIS No. PB84-155845), February 1984,
is intended to be a resource document for
the preparation and execution of a
sampling-and-analysis plan for hazard-
ous-waste incinerators. The Methods
Manual recommends a variety of analyti-
cal techniques for the determination of
POHCs. Methods were written to in-
corporate fused-silica capillary gas
chromatography/mass spectrometry
(GC/MS) and high-performance liquid
chromatography (HPLC). These methods
were designed to provide satisfactory
qualitative and quantitative analyses on a
cost-effective basis for a variety of waste
types and process chemistries. Gen-
eralized GC/MS and HPLC techniques
were developed for the determination of
as many of the POHCs as possible.
Laboratory work led systematically from
the determination of the feasibility of
developing generalized test methods to
the standardization of the resulting
methods for selected PICs and POHCs.
Initially, standard solutions of mixtures of
selected PICs and POHCs were analyzed
to optimize instrumental operating condi-
tions. Then individual chromatograms
(GC/FID and GC/MS) were obtained,
calibration curves were established, and
detection limits were estimated.
The following tasks supplemented the
development of generalized test proce-
dures and assisted workers in the area of
incineration or combustion of hazardous
waste:
• The evaluation of generalized
analysis methods for 10 PCDDs and
3 PCDFs by GC/FID and GC/MS.
• The evaluation of generalized
analysis methods for 23 non-dioxin
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proposed PICs.
• The evaluation of a GC/MS/SIM
analysis method for 7 PCDDs and 2
PCDFs.
• The evaluation of generalized
analysis methods for 56 POHCs by
GC/FID and 58 POHCs by GC/MS
from an amendment to Appendix
VIII. Part 261, 40 CFR.
• Consultation took place during these
work assignments with personnel at
LSD; at EPA's Combustion Research
Facility in Pine Bluff, Arkansas; at
Arthur D. Little, Inc.; and at EPA/
HWERL's Center Hill Facility in
Cincinnati, Ohio.
Experimental
The GC/MS generalized test method
was developed on a Hewlett-Packard
Model 5985 GC/MS data system. Com-
ponents of the instrument include a
hyperbolic quadrupole mass filter with a
convertible electron-impact (El) and posi-
tive-ion chemical-ionization source and a
capillary and jet separator GC/MS inter-
face. Its data system includes an HP2113
computer, a high-speed printer, a mag-
netic tape system, a 50-megabyte
HP7920M disk-drive system, a communi-
cations interface, GC/MS operating
software, and an unabridged NBS spectral
library. The supplemental GC/FID work
was performed on a Hewlett-Packard
Model 5840 GC that was equipped for
use with capillary columns.
The work with both the GC/MS and
GC/FID involved capillary-column chro-
matography with matched, crosslinked
fused-silica SE-54 capillary columns 25
m long with a 0.31-mm ID. The initial
operating conditions were a compromise
of those given for several capillary GC
methods in the Methods Manual. The
initial starting column temperature was
40 °C; the temperature was then pro-
grammed at 10 °C/min to 280 °C for 15
min. Alternate column temperature pro-
grams used rates of 20 and 30 °C/min.
Injection and detection temperatures were
250 °C. The carrier gas (helium) was
maintained at a flow rate through the
column of about 2 mL/min. In both the
GC/MS and the GC/FID work, the "split-
less" injection technique was employed.
Consequently, it was assumed that es-
sentially all of the injected sample reached
the column.
Having established GC operating condi-
tions by the GC/FID procedure, the
method was then applied to the deter-
mination of the candidate PICs and POHCs
by GC/MS. The mass spectrometer was
operated in a full mass scanning range
(41 to 450 amu) in the El mode. The scan
time was maintained at <1 s to enable
the collection of enough scans to char-
acterize each capillary GC peak. The mass
spectrometer was used in the selected-
ion monitoring (SIM) mode to determine
dioxins and furans.
Development of Analysis
Methods
In all. 36 PICs and 56 POHCs were
determined by GC/FID, and 36 PICs and
58 POHCs by GC/MS. Retention times
and on-column detection limits were
determined for each compound. Retention
times were measured relative to that ob-
served for the internal standard,
anthracene-d10. The on-column detection
limit was estimated using experimentally
determined calibration curves as sug-
gested in Appendix A of "Methods for
Organic Chemical Analysis of Municipal
and Industrial Wastewater." EPA-600/
4-82-057 (NTIS No. PB83-201798).
Typical values were 2 to 800 ng. From
triplicate determinations of the candidate
PICs and POHCs, relative standard devia-
tions (RSDs) were calculated, ranging
from 0.2 to 31 %. GC/MS determinations
were less precise than GC/FID deter-
minations.
Conclusions
Generalized GC/FID and GC/MS proce-
dures were successfully developed for
the determination of candidate PICs. A
selected-ion monitoring GC/MS proce-
dure for PCDDs and PCDFs was also
evaluated. Generalized GC/FID and GC/
MS procedures were extended to POHCs
from the amended Appendix VIII, Part
261, 40 CFR.
The generalized methods are suitable
for the determination of PCDDs and
PCDFs. The methods are also applicable
to substituted polycyclic aromatic hydro-
carbons (PAHs).
The developed generalized methods are
suitable for inclusion in the Methods
Manual. The methods were standardized
with selected organic compounds over
concentration ranges of interest and
showed acceptable precision in the deter-
mination of most of the compounds.
R. James. L. Farr, R. Adams, and H. Miller are with Southern Research Institute,
Birmingham, AL 35255-5305.
Larry D. Johnson is the EPA Project Officer (see below)
The complete report, entitled "PIC Analysis Methods," (Order No. PB 87-208
955/AS; Cost: $42.95, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield VA 22161
Telephone. 703-487-4650
The EPA Officer can be contacted at:
Air and Energy Engineering Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
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United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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