United States
Environmental Protection
Agency
Air and Energy Engineering
Research Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S8-87/037 Dec. 1987
&ERA Project Summary
POHC Analysis Methods for
Hazardous Waste Incineration
Ruby H. James, Joe M. Finkel, H. Kenneth Dillon, Robert E. Adams,
Herbert C. Miller, and Afaf K. Wensky
This report describes the evaluation
of generalized GC/FID, GC/MS,
HPLC/UV. and HPLC/fluorescence
analysis methods for measuring princi-
pal organic hazardous constituents
(POHCs) in various influent and effluent
streams of incineration facilities. The
report includes summary sheets that
list relative retention times, on-column
detection limits, molecular weights,
relative ion abundances, and wave-
lengths of detection for the POHCs.
Reference chromatograms, calibration
curves, mass spectra, key ions and rela-
tive abundances, and UV absorption
spectra of the POHCs are presented in
report appendices.
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 project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).
Introduction
As part of the Resource Conservation
and Recovery Act of 1976, the U.S. En-
vironmental Protection Agency has pro-
posed regulations for owners and
operators of facilities that treat hazardous
wastes by incineration to ensure that
these incinerators will be operated in an
environmentally responsible manner. The
primary criterion upon which the opera-
tional specifications are based is the
destruction and removal efficiency (DRE)
of the incinerator. The DRE value, defined
in terms of waste-input and stack-output
levels of designated principal organic
hazardous constituents (POHCs), must
be equal to or greater than 99.99%.
Approximately 400 compounds (desig-
nated POHCs) are included in Appendix
VIII, Part 261, 40 CFR. However, the
survey/analysis portion of a waste-
characterization scheme often targets
specific compounds for determination in
incinerator effluent that are not amenable
to previously developed methods. There-
fore, current research involves the
development of specific GC/FID,* GC/
MS, HPLC/UV, and HPLC/fluorescence
methods for the determination of several
of these compounds. This work involved
the evaluation of generalized GC/FID,
GC/MS, HPLC/UV, and HPLC/fluore-
scence methods for determining approxi-
mately 200 compounds from this list of
POHCs. This report presents preliminary
data on methodology for candidate POHCs
that represent a variety of compound
types, including alcohols, esters, chlori-
nated aliphatics and aromatics, carboxylic
acids, aliphatic and aromatic amines,
nitrated aromatics, nitrosamines, hydra-
zines, nitriles, organosulfur compounds,
polynuclear aromatics and heterocyclics,
and organometallics.
EPA's manual. Sampling and Analysis
Methods for Hazardous Waste Combus-
tion, EPA-600/8-84-002, is a resource
document for the preparation and execu-
tion of a sampling-and-analysis plan for
hazardous-waste incinerators. Report
EPA-600/8-84-002 recommends a vari-
ety of analytical techniques for deter-
mining POHCs. Methods were written to
incorporate fused-silica capillary GC/MS
and 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. Generalized GC/MS
GC = gas chromatography, FID = flame
ionization detection, MS = mass spectro-
metry, HPLC = high performance liquid
chromatography, and UV = ultraviolet.
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and HPLC techniques were developed to
determine as many of the POHCs as
possible.
The laboratory work was structured to
lead systematically from determining the
feasibility of developing generalized test
methods to standardizing the resulting
methods for selected POHCs. Initially,
standard solutions of mixtures of selected
POHCs were analyzed to optimize instru-
mental operating conditions. Then in-
dividual chromatograms (GC/FID, GC/
MS, HPLC/UV, HPLC/fluorescence)were
obtained, calibration curves were estab-
lished, and detection limits were
estimated.
The following tasks supplemented the
development of generalized test proce-
dures and, in general, improved EPA-
600/8-84-002:
• The evaluation of generalized analy-
sis methods for approximately 100
POHCs by GC/FID and GC/MS.
• The application of a selective GC
column and GC/MS using selected-
ion monitoring to determine 2,3,7,8-
TCDD.
• The evaluation of generalized analy-
sis methods for approximately 100
POHCs by HPLC/UV.
• The evaluation of generalized analy-
sis methods for 13 POHCs by
HPLC/fluorescence.
• The development of a derivatization
technique for three organometallic
POHCs.
• The evaluation of generalized analy-
sis methods for five organometallic
POHCs by GC/FID, GC/MS, and
HPLC/UV.
Experimental
Description of Instruments and
General Operating Conditions
The GC/MS generalized test method
was developed on a Hewlett-Packard (HP)
Model 5985A GC/MS data system. Sys-
tem components included a hyperbolic
quadrupole mass filter with a convertible
electron-impact (El) and positive-ion
chemical-ionization source and a capillary
and jet separator GC/MS interface. Its
data system included an H2113 computer,
a high-speed printer, a magnetic tape
system, a 50-megabyte HP7920M disc-
drive system, a communication interface,
GC/MS operating software, and an un-
abridged NBS special library. The supple-
mental GC/FID work was performed on a
HP Model 5840 GC equipped for use with
capillary columns.
The work with both the GC/MS and
the GC/FID involved capillary-column
chromatography with matched, cross-
linked fused-silica SE-54 capillary
columns 25 m long with a 0.31-mm ID.
The initial operating conditions were a
compromise of the conditions given for
several capillary GC methods in EPA-
600/8-84-002. The initial starting column
temperature was 40 °C; the temperature
was then programmed at 10 °C/min 280
°C for 15 min. Alternate column tem-
perature programs used rates of 20 and
30 °C/min. Injection and detection tem-
peratures 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 work and the GC/FID
work, the "splitless" injection technique
was employed. Consequently, essentially
all of the injected sample reached the
column.
The determination of 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (2,3,7,8-TCDD)
used a fused-silica capillary column
capable of separating the 2,3,7,8-TCDD
isomer from the other 21 TCDD isomers
(Chrompack CP SIL 88, 0.22-mm ID, 60-
m length). The initial column temperature
was 45 °C for 3 minutes, then pro-
grammed to 190 °C at 25 °C/min, then
programmed to 240 °C at 5 °C/min, and
held at 240 °C for 10 minutes. The injec-
tion temperature was 290 °C. Helium at
2 mL/min was used as the carrier gas.
Having established GC operating con-
ditions by the GC/FID procedure, the
method was applied to determine the
candidate POHCs by GC/MS. The MS
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
characterize each capillary GC peak. The
MS was used in the selected-ion moni-
toring (SIM) mode to determine 2,3,7,8-
TCDD. The ions monitored were m/z
257, 320, and 322 for native unlabeled
2,3,7,8-TCDD; 328 for 37C14-2,3,7,8-
TCDD; and 332 and 334 for l:»C12-2,3,7,8-
TCDD.
HPLC Analysis Procedures
The POHCs were grouped into classes
of compounds and submitted for HPLC
analysis. Initially, standard mixtures of
candidate POHCs were analyzed to
establish solvent programs suitable for
determining a variety of compounds. The
UV detector was set to monitor absorb-
ances at 254 nm. Various chromato-
graphic conditions were evaluated and
modified until the evaluation rate and the
resolution were optimized.
Ten chromatographic conditions are
described in the report. Three columns
were used in this work: HC-ODS-SIL-X-
1, AiBondapak C18, and ^Bondapak CN.
In subsequent work, the UV absorption
spectra of the candidate POHCs were
determined on a Gary Model 17 spectro-
photometer to establish an absorption
maximum in the range from 190 to 400
nm that would be a suitable alternate
wavelength for quantifying each POHC
by HPLC/UV. For HPLC/fluorescence, the
excitation wavelength was 280 nm for
the PAHs (polynuclear aromatic hydro-
carbons) and 360 nm for the aflatoxins.
Derivatization Procedure
Standards were prepared by weighing
small amounts (1.0 mg) of the three
compounds (benzenearsonic acid, hydro-
xydimethylarsine oxide, and phenylmer-
cury acetate) into 50-mL centrifuge tubes,
adding 1.0 mL of hydroiodic acid (HI) and
shaking for 1 minute. The derivatives
we re extra cted i nto 10 m L of hexa ne a nd
diluted to make standards.
Results and Discussion
GC/FID and GC/MS Analysis
The report summarizes the GC/MS
determinations of approximately 100
candidate POHCs. The retention time and
on-column detection limit are given for
each compound. The compounds are
listed in the order of their elution from
the GC column. Retention times are
relative to that observed for the internal
standard, anthracene-d10. The on-column
detection limit was estimated using the
calibration curve as suggested in Appendix
A of Methods for Organic Chemical
Analysis of Municipal and Industrial
Wastewater, EPA-600/4-82-057. Typical
values were between 0.1 and 80.0 ng.
HPLC/UV Analysis
The report summarizes the HPLC deter-
minations of approximately 100 candidate
POHCs. The retention time, on-column
detection limit, and wavelength of detec-
tion are given for each POHC. The POHCs
are listed by group in order of their elutior
from the HPLC column and subdivided b\
procedural option. Detection limits were
calculated by the same procedure used ir
GC analyses. Detection limits ranged frorr
0.001 to 6 ng. The wavelength of detectior
was 254 nm except where noted. Ar
alternate wavelength was selected frorr
the reference UV spectrum to optimize
the detection of the POHCs.
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HPLC/Fluorescence Analysis
The determination of 13 POHCs was
completed by HPLC/fluorescence. The
retention time, on-column detection limit,
and excitation/emission wavelengths are
given for each POHC. The POHCs are
listed by group in order of their elution
from the column and subdivided by proce-
dural option. The on-column detection
limit was calculated in the same manner
as used for GC/FID and GC/MS. Detec-
tion limits ranged from 0.001 to 0.4 /^g.
Conclusions
Generalized GC/FID, GC/MS, HPLC/
UV, and HPLC/fluorescence procedures
were developed to determine candidate
POHCs. Initially, standard solutions of
mixtures of selected POHCs were
analyzed to optimize instrumental oper-
ating conditions. Then individual chro-
matograms (GC/FID, GC/MS, and
HPLC/UV) were obtained, calibration
curves were established, and detection
limits were estimated. The technical
approach in developing and evaluating
the generalized instrumental methods is
discussed in the report. The chromato-
grams and data are provided in three
report appendices.
Appendix A contains the chromato-
grams and calibration curves for the
GC/FID determinations. Appendix B
shows the mass spectra in addition to the
chromatograms and calibration curves
for GC/MS determinations. Appendix C
contains the UV absorption spectra as
well as the chromatograms and calibration
curves for HPLC/UV determinations.
A simple denvatization technique al-
lows the determination of benzenearsonic
acid, hydroxydimethylarsme oxide, and
phenylmercury acetate by the generalized
GC/FID and GC/MS procedures. These
compounds were recovered quantitatively
from sorbents, filters, and water. The
derivatization procedure may be useful
for other organometallic compounds.
Compounds such as selenourea and
tetraethyl lead may be determined by the
HPLC/UV and GC/FID or GC/MS proce-
dures, respectively, without major modifi-
cations of the procedures. The deter-
mination of 2,3,7,8-TCDD by the general
GC/MS procedure provides a screening
analysis and may be applicable for sur-
vey/analysis of hazardous waste. How-
ever, ultimate selectivity and sensitivity
are provided by an isomer-specific GC
column and SIM mass spectrometry.
The developed generalized methods are
suitable for inclusion in EPA-600/8-84-
002. The methods were standardized with
selected organic compounds over con-
centration ranges of interest and showed
acceptable precision in determining most
of the compounds.
R. James. J. Finkel, and H. Miller are with Southern Research Institute,
Birmingham, AL 35255; H. Dillon is with University of Alabama, Birmingham,
AL 35294; R Adams is with Triangle Laboratories, Research Triangle Park,
NC27713, andA. Wensky is with Battelle-Columbus Laboratories, Columbus,
OH 43201.
Larry D. Johnson is the EPA Project Officer (see below).
The complete report consists of three volumes entitled "POHC Analysis Methods
for Hazardous Waste Incineration."
Volume 1, Part 1 (Order No. PB 87-227 286/AS, Cost $3095, subject
to change).
Volume 1. Part 2 (Order No. PB 87-227 294/AS, Cost $3695, subject
to change).
Volume 2 (Order No. PB 87-227 302/AS, Cost $24 95, subject to change)
The above reports 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
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