United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-84-029 May 1984
&EPA Project Summary
Report on Analytical
Methodology for Purgeable and
Semivolatile Components in
Leachates and Solid Wastes
J. S. Warner, M. C. Landes, P. W. Meehan, R. L. Wilson, and T. H. Danison
Methods to determine purgeable and
semivolatile organic compounds in
solid wastes were studied. Extraction
efficiencies, method quantification
limits, and matrix effects were studied
for 57 volatile and 142 semivolatile
contaminants in a variety of solid waste
matrices. Recoveries of spiked
compounds were in the 90 to 100%
range except for the highly polar
materials for which poor recovery could
be expected . The quantitation limits
were found to be 5 fjg/g or less for
about 90% of the compounds and 1
fjg/g or less for half of the compounds.
Some significant matrix effects were
detected in two sample type. The
effects were both compound and
matrix dependent and could not be
predicted.
For purgeable compounds, the tetra-
glyme method gave results comparable
to the Speis heated purge and trap
method, and was superior to the
aqueous dispersion method. Methyl
tert-butyl ether was not as efficient as
methylene chloride for the extraction of
semivolatile organics in some
lipophobic wastes. The tetraglyme and
methylene chloride extraction methods
are recommended for analyzing
organics in solid wastes and solid waste
leachates.
This Project Summary was developed
by EPA's Environmental Monitoring
and Support Laboratory. Cincinnati,
OH, to announce key findings of the
research project that is fully document-
ed in a separate report of the same title
(see Project Report ordering informa-
tion at back).
Introduction
Under the Resource Conservation and
Recovery Act, the U.S. Environmental
Protection Agency is responsible for
assessing the potential hazard of
municipal and industrial solid wastes.
The organic chemical content of waste is
one of the characteristics used to assess
the potential hazard associated with
waste disposal. In a recent investigation
conducted by Battelle-Columbus Labora-
tories, analytical methodology was devel-
oped to determine purgeable and semi-
volatile organic compounds in solid
wastes. Two extraction and gas chroma-
tography/mass spectrometry (GC/MS)
methods were developed and applied to a
variety of solid wastes in an interlabora-
tory study. The program described in this
report was undertaken to provide
additional supporting data related to the
application of these methods to the
analysis of solid wastes and solid waste
leachates, and to demonstrate the
methods' effectiveness relative to other
widely accepted procedures used to
extract and analyze purgeable and semi-
volatile organic components.
For purgeable compounds, the
tetraglyme extraction method is demon-
strated and compared to the Speis heated
purge and trap method and the aqueous
dispersion method. Semivolatile com-
pounds were extracted with methylene
chloride or methyl tert-butyl ether
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(MTBE). QuantitationbyGC/MS, GCwith
flame ionization detection (GC-FID), and
microcoulometric total organic halide
(TOX) techniques were investigated.
Each method was evaluated by
determining the extraction efficiency of
the solvent, matrix effects, and method
quantification limits.
Purgeable Organic Methods
The three methods compared for
purgeable organics were identical in the
analysis phase, but differed significantly
in the sample preparation and purge
technique. The tetraglyme extraction
method involved the extraction of 2
grams of wastewith 40 ml_ of tetraglyme
and the addition of 1 to 1000 /jL of the
extract to a purge tube. The Speis method
involved the purge of a neat sample of
waste in a sand bath at 80°C. The purge of
very small samples was necessary to
avoid overloading the chromatographic
system by high levels of organics. The
aqueous dispersion method involved
adding 1 to 5 grams ofwaste to deionized
water to give a dispersion of approximate-
ly 1 % solids, and adding an aliquot of the
dispersion to a purging tube.
Semivolatile Organics
Methylene chloride was used in the
neutral sonif ication extraction method for
extracting solid wastes because it is
known to be a good solvent for a wide
variety of organic compounds. Methylene
chloride extracts are readily analyzable by
GC/MS, however, they cannot be used
with other specific GC detectors such as
electron capture, thermionic, or TOX
detectors. For those applications, MTBE
was proposed as an alternate solvent.
Samples of six wastes were spiked and
extracted with .methylene chloride and
MTBE. Aliquots of each extract were
dried and the residue weights recorded.
The masses of the residues found in the
extracts show clearly that MTBE is not as
effective as methylene chloride under the
conditions used. MTBE was found to be
effective for the extraction of lipophilic
wastes, but not effective for lipophobic
wastes. Recoveries of individual
components also varied extensively
within a given waste, showing compound
dependency of extraction.
Method quantification limits for
various semivolatile compounds
extracted with methylene chloride were
expected to vary depending on the
detector sensitivities and the compounds'
interaction with the waste matrix. In
order to decrease the matrix interactions,
the previously described kaolin/diatoma-
ous earth wet mud was used. Aliquots of
the mud were spiked with 142
semivolatile organic compounds at three
spike levels, over a range of 1 to 25 /ug/g.
A fourth spike level of 125 fjg/g was
tested for 107 of the more soluble
compounds. The spiked samples were
extracted, concentrated, and analyzed by
GC/MS. Each of the 142 compounds was
quantified using the internal standard
approach. For 79 semivolatiles, the
estimated quantification limit was 1 fjg/g
or less, while for another 54 compounds
the range was 2 to 5 fjg/g. Higher
quantification limits were generally
found for the more polar compounds;
however, even for the most polar
compounds such as phenols, anilines,
and nitro compounds, the estimated
quantification limits were about 5 /jg/g.
The only compounds which could not be
quantified at the 10 /ug/g level were
thiophenol, 4-bromobenzoic acid, 4-
nitrophenol, 2,4-D,2,4,5-T, and diethyl-
stilbestrol.
In each method, the organics were
purged and concentrated on a Tenax trap
which was then thermally desorbed. The
effluent was analyzed in accordance with
EPA Methods 601 and 602. In general,
the amounts of organics found by the
Speis method were similar to those from
the tetraglyme method, but the amounts
found by the aqueous dispersion method
were often considerably less than the
tetraglyme method.
The determination of method
quantification limits for the purgeable
organics using the tetraglyme method
was carried out under conditions selected
to avoid strong interaction between the
solid matrix and the organic
contaminants. An organic-free mixture of
kaolin and diatomaceous earth was
produced and fully hydrated with organic-
free water to form a mud-like sample.
Aliquots of the wet mud were spiked with
57 volatile organic compounds at four
levels ranging from 1 to 125 fjg/g of
waste. Each spiked aliquot was extracted
with tetraglyme and analyzed by purge
and trap GC/MS. Individual compounds
were identified by a computer search
technique and quantified by comparison
to calibration runs at the same levels.
Percent recoveries for the volatile
organics from the matrix were 100 ±
25%. The results also indicated that
purging efficiency was not affected by
addition of up to 4% tetraglyme to 5 mLof
water in the purge solution.
Method quantification limits for 28 of
the 57 compounds were 1 fjg/g ofwaste
or less, and for another 17 compounds
the quantitation limits were 2 to 5
As expected, the quantification limits
were for very polar water-soluble
compounds were higher, but most were
determined to be less than 25 jug/g. Only
three compounds, epichlorohydrin,
dichloroacetonitrile, and vinyl acetate,
could not be quantified at the 25 fjg/g
level.
Matrix effects due to the coextraction of
nonpurgeable compounds were studied
to determine what effect the additional
compounds have on the purging
efficiency. Tetraglyme extracts of nine
wastes were analyzed with and without
spiking of 12 representative purgeable
organics. Extracts were analyzed by GC
with photoionization detector (PID)or Hall
detector, and also by Dohrmann micro-
coulometric purgeable organic halogen
(POX) analyzer. The methods provided
similar results, but were too variable to
detect any matrix effect in the GC-
PID/Hall system. The POX method
provided more precise data, and no sig-
nificant matrix effects were observed.
Percent recoveries obtained for
compounds spiked at the 25 /ug/g level
were determined by comparing peakarea
analyte: internal standard ratios with
those obtained from the corresponding
calibration solution. The recoveries were
90 ± 20% for the majority of all
compounds.
A study of matrix effects attributed to
the total extractable mass was under-
taken. Extracts of nine waste materials—
both spiked and unspiked—were analyzed
by microcoulometric TOX analysis and by
GC-FID. For the TOX analyses, spike
recoveries were 87 to 99% and were not
significantlydifferentfrom spiked blanks.
It was concluded that nosignificant matrix
effects were attributable to the waste
matrix. Recoveries of spiked compounds
by GC-FID were also generally in the
same range. However, in two cases,
significant matrix effects were detected.
These effects were both compound de-
pendent and matrix dependent and could
not be readily predicted.
Discussion of Results
The data demonstrated the applicability
of the tetraglyme extraction and
methylene chloride extraction methods to
the analysis of purgeable and
semivolatile fractions of solid waste and
solid waste leachates. The tetraglyme
extraction method provided results which
were comparable to the Speis method for
analyzing purgeables and superior to the
aqueous dispersion method results. For
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semivolatile compounds, the methylene
chloride extraction procedure provided
excellent recoveries and few significant
matrix effects. With few exceptions,
notably the very polar, water-soluble
compounds, the quantification limits for
both classes of compounds were esti-
mated to be less than 5 /ug/g of waste.
Therefore, the tetraglyme and methyl-
ene chloride extraction procedures are
recommended for determining purgeable
and semivolatile organic compounds in
solid wastes and solid waste leachates.
J. S. Warner, M. C. Landes, P. W. Meehan, R. L. Wilson, and T. H. Danison are with
Banelle Columbus Laboratories, Columbus, OH 4320T.
Robert W. Slater is the EPA Project Officer (see below).
The complete report, entitled "Report on Analytical Methodology for Purgeable
and Semivolatile Components in Leachates and Solid Wastes," (Order No. PB
84-18O 157; Cost: $11.50. 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 Project Officer can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
U.S GOVERNMENT PRINTING OFFICE; 1984 — 759-015/7699
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Environmental Protection
Agency
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Information
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