United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory
Las Vegas NV 89114
Research and Development
EPA/600/S4-85/082 Jan. 1986
v>EFV\ Project Summary
Single-Laboratory
Evaluation of the RCRA
Method for Analysis of Dioxin in
Hazardous Waste
F. L. Shore, T. L. Vonnahme, C. M. Hedin, J. R. Donnelly, W. J. Niederhut, and S.
Billets
Single laboratory testing of RCRA
Method 8280 for the determination of
chlorinated dibenzo-p-dioxinsand -fur-
ans has been initiated on sample ma-
trices including pottery clay, Missouri
soil, fly ash, a still bottom from a
chlorophenol-based herbicide produc-
tion process, and an industrial process
sludge. This method was intended for
the analysis of chlorinated dioxin and
dibenzofuran homologs with four, five,
or six chlorine atoms per molecule.
Revisions to the method, which were
found necessary for satisfactory per-
formance, have been tested and incor-
porated into a revised version of the
method.
Single laboratory testing of Method
8280 incorporating minor revisions
provided satisfactory performance for
the target analytes in soil and fly ash
samples. Further modification and elab-
oration of sample cleanup procedures
were necessary for the analysis of the
still bottom and industrial sludge sam-
ples.
This Project Summary was developed
by EPA's Environmental Monitoring
Systems Laboratory, Las Vegas, NV, to
announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
In part, as a result of finding trace levels
of 2,3,7,8-tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD) as a contaminant in com-
mercial preparations of chlorophenol-
based herbicides, the U.S. EPA initiated
(in 1973) monitoring efforts for 2,3,7,8-
TCDD in environmental samples. Later
findings of contamination by 2,3,7,8-
TCDD in soil samples from Niagara Falls,
New York, and various sites in Missouri
led to extensive sampling and analysis
efforts. It is now known that many, if not
all, of the 75 possible chlorinated dioxins
and 135 structurally related chlorinated
dibenzofurans possess relatively high
toxicities to man and certain animal
species. Most available acute and chronic
toxicological data for chlorinated dioxins
and dibenzofurans are based upon the
2,3,7,8-TCDD isomer. In certain animal
species (notably, the guinea pig), extra-
ordinarily low doses may be lethal. As
such, these compounds are considered to
be among the most potent man-made
toxicants. Exposure to these compounds
has been observed to produce a wide
range of systemic effects including hep-
atic disorders, carcinoma, and teratogen-
icity in certain animal species, although
the major documented effect upon hu-
mans has been chloracne.
The EPA has determined that enhanced
toxicities are likely to be observed with
samples containing tetra-, penta-, and
hexa-chlorinated dioxins and dibenzofur-
ans (40 CFR 261, 1978, January 14,
1985). In 1983 (40 CFR 65,14514, April
4, 1983), the EPA proposed a ruling
affecting disposal of hazardous wastes
containing tetra-, penta-, and hexa-chlor-
inated dioxins and dibenzofurans. These
-------
wastes would be managed under the
Resource Conservation and Recovery Act
(RCRA) and would be analyzed for the
target chlorinated dioxins and dibenzo-
furans using an analytical method which
was included as an Appendix to the
proposed rule.
In order to manage these wastes ef-
fectively, it is necessary to obtain data
regarding the performance of the method
included in the Federal Register on rele-
vant waste samples. This study was
intended to determine and elaborate any
changes needed for satisfactory method
performance and to provide method per-
formance data after any revisions had
been made. Hazardous waste sample mat-
rices which have been subjected to
analysis under this method include soils,
a carbonaceous material (fly ash), a
chlorophenol production still bottom, and
an industrial sludge.
This report summarizes results ob-
tained under a single-laboratory evalua-
tion. The final revised method has been
shown to perform well on a number of
sample types.
Study Design
RCRA Method 8280 for the analysis of
chlorinated dibenzo-p-dioxins and dibenzo-
furans consists of 4 major sections: (1)
extraction of the analytes from the sam-
ple; (2) "open" column chromatographic
cleanup with alumina using a methylene
chloride/hexane eluent; (3) HPLC clean-
up; and (4) analysis by high resolution gas
chromatography/low resolution mass
spectrometry (HRGC/LRMS). In order to
test the method and to develop appro-
priate modifications with minimal redun-
dancy, each section of the procedure was
tested separately. Initial tests were per-
formed on a simple (pottery clay soil)
sample matrix and upon standard solu-
tions. Only after adequate method per-
formance data was achieved on such
materials, was the analysis of more
complex samples investigated. The first
step to be elaborated was the measure-
ment technique. Both HRGC/LRMS and
HRGC/ECD (electron capture detection)
were tested, using guidelines from the
published RCRA method. Given the re-
quirements of the detector, the cleanup
steps were then studied in detail and
appropriate modifications were investi-
gated and documented. Additional eval-
uation of this method involved a sys-
tematic investigation of each critical
phase. This procedure allowed for a
separate description of each section of
the method to document any recommend-
ed modification.
Results
The principal types of revisions which
were made to the original method include:
(1) the addition of a carbon column
cleanup procedure to eliminate closely
related chemical species; (2) revision of
the alumina column elution pattern so
that all desired analytes eluted in a single
fraction, with the bulk of the analytical
interferences removed; (3) changes in the
sample preparation procedures so that
wet samples could be accommodated;
and (4) addition of HPLC procedures that
could be reproducibly and effectively
performed.
The RCRA method with revisions dis-
cussed above, was subjected to perform-
ance tests which included (1) analysis of
reference materials containing 2,3,7,8-
TCDD and interferences; (2) precision and
accuracy determinations on samples hav-
ing known composition obtained by spik-
ing the sample matrix.
Performance of the revised method
was documented through precision and
accuracy determinations (standard dev-
iation of results), by recovery of spiked
analytes and isotopically-labeled stand-
ards, and by using two independent
teams of analysts.
After incorporating necessary revi-
sions, satisfactory method performance
has been demonstrated on RCRA type
samples. Performance of the method on
relativley complex matrices, such as
sludges, still bottoms, and fly ash, has
been determined and precision and ac-
curacy data are summarized in Tables 1
and 2.
Table 1. Precision Data for Revised Method 8280
Compound
2,3,7, 8 -TCDD
1,2,3,4-TCDD
1,3,6,8-TCDD
1,3.7, 9 -TCDD
1,3,7,8 -TCDD
1.3,7. 8 -TCDD
1.2.8.9-TCDD
1,2.3.4, 7-PeCDD
Matrix*
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
flyash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Analyte Level (ng/gl
Native
Native + Spike N
NO*
378
NO
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
422
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
25.8
ND
5.0
378
125
46
487
5.0
25.0
125
38.5
2500
2.5
25.0
125
19.1
2727
2.5
25.0
125.0
58.4
2500
5.0
25.0
125
16.0
2920
5.0
25.0
125
2.6
2500
5.0
25.0
125
46
2500
5.0
25.0
125
25.8
2500
4
4
4
2
4
3
4
4
4
4
4
4
4
2
2
4
4
4
2
2
4
4
4
4
2
4
4
4
3
2
4
4
4
2
2
4
4
4
2
2
Percent
USD
4.4
2.8
4.8
--
24
1.7
1.1
9.0
7.9
--
7.0
5.1
3.1
—
—
19
2.3
6.5
--
-
7.3
1.3
5.8
3.5
-
7.7
9.0
7.7
23
—
10
0.6
1.9
—
—
10
2.8
4.6
6.9
--
-------
Table 1. (Continued)
Analyte Level (ng/gj
Native Percent
Compound Matrix* Native + Spike N RSD
1,2.3,7,8-PeCDD clay NO 5.0 4 25
soil NO 25.0 4 20
sludge ND 125 4 4.7
fly ash ND 46 2
still bottom ND 2500 2
1.2.3.4,7,8-HxCDD clay ND 5.0 4 38
soil NO 25.0 4 8.8
sludge ND 125 4 3.4
fly ash ND 46 2
still bottom ND 2500 2
1.2,3.4.6.7.8-HpCDD clay ND 5.0 4
soil ND 25.0 4
sludge3 8760 8780 4
fly ash ND
still bottom ND
1.2.7.8-rCDF clay ND 5.0 4 3.9
soil ND 25.0 4 1.0
sludge ND 125 4 7.2
fly ash 7.4 7.4 3 7.6
still bottom ND 2500 2
1, 2.3.7. 8-PeCDF clay ND 5.0 4 6.1
soil ND 25.0 4 5.0
sludge ND 125 4 4.8
fly ash ND 46 2
still bottom3 25600 28100 2
1. 2.3.4,7.8 -HxCDF clay ND 5.0 4 26
soil ND 25.0 4 6.8
sludge 13.6 139 4 5.6
fly ash 24.2 24.2 4 13.5
still bottom ND 2500 2
OCDF clay ND
soil ND
sludge 192 317 4 3.3
fly ash ND
still bottom ND
^matrix types:
clay: pottery clay, Westwood Ceramic Supply Co., City of Industry, California.
soil: Times Beach, Missouri. Soil was blended to form a homogeneous sample. This sample was
analyzed as a performance evaluation sample for the Contract Laboratory Program (CLP) in April
1 983. The results from EMSL -L V and 8 contract laboratories using the CLP protocol were 305. 8
ng/g 2.3,7, 8-TCDD with a standard deviation of 81.0.
fly ash: ash from a municipal incinerator designated as resource recovery ash No. 1 .
still bottom: distillation bottoms (tar) from 2,4-dichlorophenol production obtained from Arthur D.
Little, Inc., 1983.
sludge: sludge from cooling tower which received both creosote and pentachlorophenolic
wastewaters.
Cleanup of clay, soil and fly ash samples was through the alumina column only. (Carbon column
not used.)
2ND — not detected at concentration injected (final volume 0. 1 ml or greater).
Estimated concentration out of calibration range of standards.
Matrix Analysis mended method A 50ng spike of 2,3,7,8-
A pottery clay sample was selected as a TCDD was added, and extraction was
model matrix for determining extraction performed as specified in the un re vised
efficiency obtained following the recom- method. This experiment was performed
in triplicate, and a similar experiment was
performed in triplicate on wet pottery clay
(i.e., 5.0 g clay, and 5.0 g water). Per-
formance of the extraction procedure was
solvent system was developed. This mod-
ified procedure adds methanol and sod-
ium sulfate to the petroleum ether solvent
specified in the method and uses a
Kuderna-Danish concentration tech-
nique Performance was improved on
both dry and wet samples and the revised
extraction procedure resulted in satisfac-
tory overall method performance (e.g.,
dioxin surrogate spike recovery values).
A representative sample of pottery clay
was spiked with suitable interferences
and with analytes of interest (PCDD's and
TCDF) to determine method performance
on a clean soil matrix. Interferences such
as Silvex, DDE, and Aroclor 1260 were
used at concentrations from 10 to 200
times that of each target analyte. Separa-
tion of interferences in clay samples was
achieved.
A portion of a municipal incinerator fly
ash material was obtained in order to
provide an environmental carbonaceous
type matrix for testing. This type of sample
zene extraction with a Soxhlet apparatus
to remove absorbed dioxins nd dibenzo-
furans. These analytes are often found in
such samples at high ppt to low ppb
levels. Therefore, it was decided to spike
such a sample with 13Ci2-2,3,7,8-TCDD
and analyze by revised Method 8280. At
the worst, a synthetic dioxin sample
would be characterized and at the best a
quantitative analysis would be performed
to determine the levels of environmentally-
incorporated dioxins and furans, using an
isotopically-labeledTCDD internal stand-
ard. Results of the HRGC/LRMS analysis
indicated the presence of numerous
"native" PCDD's and PCDF's, in addition
to a variety of other compounds at higher
levels. Recovery of the isotopically labeled
TCDD (spiked into the sample at a con-
centration to 500 pg/g) was 90 percent,
using toluene/Soxhlet/revised Method
8280.
A still bottom sample from a chloro-
phenol production process was obtained
for use as a complex waste sample. The
sample had been characterized by an
independent laboratory, which reported
detectable concentrations of some PCDD's
and PDCF's. Historically, these samples
have been most difficult to analyze for
dioxins and dibenzofurans. Due to pres-
ence of massive amounts of analytical
interferences, poor reproducibility, low
recovery of spiked PCDD's and PCDF's,
3
-------
Table 2. Recovery Data for Revised Method 8280
Native2
Compound Matrix1 (ng/g)
2.3,7,8-TCDD
1.2.3.4 -TCDD
1,3,6.8-TCDD
1,3.7.9-TCDD
1,3.7.8-TCDD
1.2.7.8-TCDD
1,2,8.9-TCDD
1. 2,3.4.7 -PeCDD
1.2,3,7,8-PeCDD
1 ,2.3,4.7.8-HxCDD
1,2.3.4,6,7.8-HpCDD
2,3,7,8-TCDD
(C-J3)
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludoe
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge4
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
ND
378
ND
ND
AQ7
4o/
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
615
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Am
ND
8780
ND
ND
ND
ND
ND
ND
ND
Spiked*
Level
(ng/g)
5.0
--
125
46
5.0
25.0
125
46
2500
2.5
25.0
125
46
2500
2.5
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
oir /l
Zo.U
125
__
5.0
25.0
125
46
2500
Mean
Percent
Recovery
61.7
-
90.0
90.0
67.0
60.3
73.1
105.6
93.8
39.4
64.0
64.5
127.5
80.2
68.5
61.3
78.4
85.0
91.7
68.0
79.3
78.9
80.2
90.5
68.0
75.3
80.4
90.4
88.4
59.7
60.3
72.8
114.3
81.2
58.4
62.2
79.2
102.4
81.8
61.7
68.4
81.5
104.9
84.0
46.8
65.0
81.9
125.4
89.1
ND
A/n
Art/
__
64.9
78.8
78.6
88.6
69.7
and relatively poor detection limits are
common. Nonetheless, this challenging
sample represents a sample type likely to
be encountered as a RCRA waste. This
sample may be described as having
effectively totally potential interferences.
since it dissolved in toluene readily, and
at least partially in hexane. Full-scan
HRGC/LRMS using a 30 m DB-5 nonpolar
column was performed in order to obtain
partial sample characterization. Through
this work and later multiple ion detection
(MID) HRGC/LRMS studies using CP-Sil-
88 and SP-2250 columns, chlorinated
phenols, diphenyl ethers, and hydroxydi-
phenylethers("pre-dioxins") were found.
along with the target analytes. Apparently
it is common on all GC columns tested for
dioxins, dibenzofurans, and diphenyl e-
thers to co-elute, complicating the mass
spectral analysis. Careful interpretation
of spectra and retention times of stand-
ards is necessary to avoid misidentifying
diphenyl ethers, benzylphenyl ethers, or
hydroxydiphenylethers having similar
m/z ion clusters as target PCDD's or
PCDF's.
Because of the limited success of the
revised RCRA Method 8280 towards
analysis of this sample, an additional
cleanup step, using a silica Spherisorb/
PX-21 charcoal column was incorporated
into the procedure. With this modification
acceptable recoveries and precision were
obtained for even the most complex
samples.
A sludge sample was obtained by the
EPA from a cooling tower which receives
both creosote and pentachlorophenolic
wastewaters. This sample contained a
high percentage of water (76 percent) and
rivaled the chlorophenol still bottom
sample in complexity of the solvent
extractable organic fraction. The water
was removed by azeotropic distillation
with toluene and the toluene extract was
then used for analysis of the PCDD's and
PCDF's. This extract was cleaned up using
the modified RCRA Method 8280 proce-
dure, which included the use of the silica
Spherisorb/PX-21 charcoal column.
This study has been completed on a
limited number of matrix and sample
types; the results show that the revised
Method 8280 provides good recovery of
the internal standard, Ci2 - 2,3,7,8 -
TCDD and the target PCDD and PCDF
analytes. The proposed cleanup proce-
dures were shown to be effective in
dealing with complex matrix problems.
An interlaboratory comparison study of
the revised method is expected to provide
additional method performance informa-
tion.
-------
Table 2. (Continued)
Compound
1,2,7,8-TCDF
1,2,3, 7,8-PeCDF
1,2.3.4,7.8-HxCDF
OCDF
Matrix^
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Native2
Ing/g)
ND
ND
ND
7.4
ND
ND
ND
ND
ND
25,600
ND
ND
13.6
24.2
ND
ND
ND
192
ND
ND
Spiked3
Level
ing/g)
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
—
--
125
--
--
Mean
Percent
Recovery
65.4
71.1
80.4
90.4
104.5
57.4
64.4
84.8
105.8
--
54.2
68.5
82.2
91.0
92.9
--
--
86.8
-
--
^matrix types:
clay: pottery clay, Westwood Ceramic Supply Co., City of Industry, California.
soil: Times Beach, Missouri. Soil was blended to form a homogeneous sample. This sample was
analyzed as a performance evaluation sample for the Contract Laboratory Program (CLP) in April
1983. The results from EMSL-LV and 8 contract laboratories using the CLP protocol were 305.8
ng/g 2,3,7,8-TCDD with a standard deviation of 81.0.
fly ash: ash from a municipal incinerator designated as resource recovery ash No. 1.
still bottom: distillation bottoms (tar) from 2,4 -dichlorophenolproduction obtained from Arthur D.
Little, Inc., 1983.
sludge: sludge from cooling tower which received both creosote and pentachlorophenolic
wastewaters.
The clay, soil and fly ash samples were subjected to alumina column cleanup, no carbon column
was used
2Final volume of concentrate 0.1 ml or greater, ND means below quantification limit, 2 or more
samples analyzed.
3Amount of analyte added to sample, 2 or more samples analyzed.
'Estimated concentration out of calibration range of standards.
.S. GOVERNMENT PRINTING OFFICE:1986/646-l 16/20755
-------
F. L Shore, T. L. Vonnahme, C. M. Hedin. J, R. Donnelly, and W. J. Niederhut are
with Lockheed Engineering and Management Services Company, Inc., Las
Vegas, NV 89114; the EPA author S. Billets (also the EPA Project Officer, see
below) is with the Environmental Monitoring Systems Laboratory. Las Vegas,
NV89114.
The complete report, entitled "Single-Laboratory Evaluation of the RCRA Method
for Analysis of Dioxin in Hazardous Waste," (Order No. PB 86-135 175/AS;
Cost: $16.95, 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 Project Officer can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Las Vegas, NV 89114
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
EPA/600/S4-85/082
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