United States
                     Environmental Protection
 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).

                       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.

and HPLC techniques were developed to
determine  as many of the  POHCs as
  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
  The following tasks supplemented the
development of  generalized test  proce-
dures and, in general, improved EPA-
   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-
   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
   The development of a derivatization
    technique for three organometallic
   The evaluation of generalized analy-
    sis methods for five organometallic
    POHCs  by  GC/FID, GC/MS, and

 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
  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-
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.

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.

  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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