United States
Environmental Protection
Agency
Research and Development
Environmental Monitoring
Systems Laboratory
P.O. Box 15027
Las Vegas NV 89114-5027
EPA-600/4-85/062
November 1985
Single-Laboratory
Evaluation of the
RCRA Method for
Analysis of Dioxin
in Hazardous Waste
prepared for the
Office of Solid Waste
-------
SINGLE-LABORATORY EVALUATION OF THE RCRA METHOD
FOR ANALYSIS OF DIOXIN IN HAZARDOUS WASTE
by
F. L. Shore, T. L. Vonnahme, C. M. Hedln, J. R. Donnelly and W. J. Niederhut*
Lockheed Engineering and Management Services Company, Incorporated
Las Vegas, Nevada 89114
~Current address Environmental Research Center, Quality Assurance
Laboratory, University of Nevada, Las Vegas, NV 89154
Contract Number 68-03-3050
Project Officer
Stephen Billets
Quality Assurance Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89114
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89114
-------
NOTICE
The Information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under Contract Number 68-03-3050
to the Lockheed Engineering and Management Services Company, Incorporated, Las
Vegas, Nevada. It has been subject to the Agency's peer and administrative
review, and 1t has been approved for publication as an EPA document. Mention
of trade names or comnerclal products does not constitute endorsement or recom-
mendation for use.
11
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FOREWORD
Largely as a result of finding trace levels of 2,3,7,8-tetrachloro-
d1benzo-p-d1ox1n (2,3,7,8-TCDD) as a contaminant 1n commercial preparations
of chlorophenol-based herbicides, the U.S. Environmental Protection Agency
(EPA) Initiated (1n 1973) monitoring efforts for 2,3,7,8-TCDD 1n environmental
samples. Later findings of contamination by 2,3,7,8-TCDD 1n soil samples from
Niagara Falls, New York, and numerous sites 1n Missouri led to extensive sampling
and analysis efforts. It 1s now known that many, 1f not all, of the 75 possible
chlorinated dloxlns and 135 structurally related chlorinated dlbenzofurans
possess relatively high toxicity to man and certain animal species. Most of
the available acute and chronic toxlcologlcal data for the chlorinated dloxlns
and dibenzofurans 1s based upon the 2,3,7,8-TCDD isomer. In certain animal
species (notably, the guinea pig), extraordinarily low doses may be lethal. As
such, these compounds are considered to be the most potent man-made toxicants.
Exposure to these compounds has been observed to produce a wide range of systemic
effects including hepatic disorders, carcinoma, and teratogenicity 1n certain
animal species, although the major documented effect upon humans has been
chloracne.
The EPA has determined1 that enhanced toxicities are likely to be observed
with samples containing tetra-, penta-, and hexa-chlorlnated dloxlns and dlbenzo-
furans. In 1983,2 the EPA proposed a ruling affecting disposal of hazardous
wastes containing tetra-, penta-, and hexa-chlorlnated dloxlns and dlbenzofurans.
These wastes would be managed under the Resource Conservation and Recovery Act
(RCRA) and would be analyzed for the target chlorinated dloxlns and dlbenzo-
furans using an analytical method which was Included as an Appendix to the
proposed rule (method 8280).
In order to manage these wastes effectively, 1t Is necessary to obtain
data regarding the performance of the method as proposed 1n the Federal
Register for the analysis of dloxln- and furan-conta1n1ng wastes. This stu
-------
ABSTRACT
Single-laboratory testing of RCRA Method 8280 for the analysis of chlori-
nated d1benzo-p-dioxins and dlbenzofurans has been initiated on sample matrices
including pottery clay soil, a Missouri soil, a fly ash, a still bottom from
a chlorophenol-based herbicide production process, and an Industrial process
sludge. This analytical method was Intended for use 1n the determination of
chlorinated dioxin and dlbenzofuran homologs with four, five, or six chlorine
atoms per molecule. Revisions to the method that were found necessary for
satisfactory analytical performance have been developed and have been Incorpo-
rated Into a revised version of the method.
Single-laboratory testing of method 8280 with minor revisions demonstrated
satisfactory performance for the target analytes on soil and fly ash samples.
Further modification and elaboration of sample cleanup procedures were necessary
for analysis of the still bottom and Industrial sludge samples.
1v
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TABLE OF CONTENTS
Page
Foreword 111
Abstract 1v
Figures v1
Tables v11
Abbreviations v111
Acknowledgment 1x
1. Introduction 1
2. Conclusions 2
3. Recommendations 3
4. Extraction Method Development and Revisions 4
5. Development of Alumina Cleanup Procedure 6
6. Elaboration of HPLC Cleanup Procedure 14
7. Analysis of Pottery Clay Samples 16
8. Analysis of Native Missouri Soil Samples 19
9. Analysis of Fly Ash Samples 20
10. Analysis of Chlorophenol Still Bottom Samples 22
11. Analysis of Sludge Samples 24
12. Rationale for Proposed Method Modifications 27
References 30
Appendices
A. RCRA Method 8280 with Revisions Based on Single-Laboratory
Testing: Method of Analysis for Chlorinated D1benzo-p-
dioxins and Dibenzofurans 31
B. Homogen1zat1on and Characterization of Resource Recovery
Fly Ash No. 1 54
v
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FIGURES
Number Page
1 HPLC analysis of analyte standard mixture 11
2 HPLC analysis of analyte standard mixture spiked with
Interference mixture (10% CHgClg/hexane fraction
from alumina column) 12
3 HPLC analysis of analyte standard mixture spiked with
Interference mixture (60% CH2Cl2/hexane fraction
from alumina column) 13
4 HRGC/MS detection of TCDD's and TCDF's 1n fly ash sample. ... 21
5 Mass chromatogram of sludge sample prior to silica
Spherisorb/PX-21 charcoal column cleanup 25
6 Mass chromatogram of sludge sample after silica
Spher1sorb/PX-2l charcoal column cleanup 26
vl
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TABLES
Number Page
1 Performance of Unrevlsed Method 8280 4
2 Soil Extraction Method Development: RCRA Method as
Published Versus Revised Extraction Procedure 5
3 Elutlon of Analytes from Basic Alumina
(per Unrevlsed RCRA Method 8280) 7
4 Elutlon of Analytes from Basic Alumina (5 percent, 20 percent,
60 percent CH2Cl2/hexane) 7
5 Elutlon of Analytes from Basic Alumina (10 percent, 60 percent
CH2Cl2/hexane) .... 8
6 Elutlon of Analytes from Neutral Alumina (Woelm Super 1)
(10 percent, 20 percent, 60 percent CH2Cl2/hexane) 8
7 Elutlon of Analytes from Neutral Alumina (Woelm Super 1)
(10 percent, 60 percent CH2Cl2/hexane) 9
8 Elutlon of Analytes from Woelm Super 1 Neutral Alumina
Deactivated with 1 Percent Water 9
9 Elutlon of Analytes from Woelm Super 1 Neutral Alumina
Deactivated with 4 Percent Water 10
10 Typical HPLC Retention Times of Potential Interferences 15
11 Analyte Percent Recoveries from Pottery Clay Samples (HRGC/EC) . 17
12 Analysis of Performance Evaluation Samples Obtained from
Contract Laboratory Program, Using Revised RCRA Method 8280. . 18
13 Directed Analyses Summary: 2,4-D and 2,4-DIBE Herbicide
Distillation Still Bottoms 23
v11
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LIST OF ABBREVIATIONS
CLP
-
Contract Laboratory Program
DL
-
detection limit
GC/EC
-
gas chromatography/electron capture detection
GC/MS
-
gas chromatography/mass spectrometry
HpCDO
-
heptachlorodibenzo-p-dloxi n (hepta-CDD)
HpCDF
_
heptachlorodlbenzofuran (hepta-CDF)
HPLC
-
high performance liquid chromatography
HRGC
-
high resolution gas chromatography
HxCOD
-
hexachlorodibenzo-p-diox1n (hexa-CDD)
HxCDF
hexachlorodlbenzofuran (hexa-CDF)
LRMS (or MS)
_
low resolution mass spectrometry
MID
-
multiple ion detection
OCDD
-
octachlorodibenzo-p-dioxi n
OCDF
-
octachlorodi benzofuran
PCDD
-
polychlorodlbenzo-p-d1oxi n
PCDF
-
polychlorodi benzofuran
PeCDD
-
pentachlorodibenzo-p-dioxi n (penta-CDD)
PeCDF
-
pentachlorodi benzofuran (penta-CDF)
PPb
-
parts per billion
ppt
-
parts per trillion
RIC
_
reconstructed 1on chromatogram
TCDD
-
tetrachlorodibenzo-p-diox1n (tetra-CDD); often used for
the 2,3,7,8-TCDD isomer
TCDF
-
tetrachlorodibenzofuran (tetra-CDF)
m/z
-
mass to charge ratio
vii 1
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ACKNOWLEDGMENT
The authors wish to thank M1ke Doubrava of Lockheed Engineering and
Management Services Company, Incorporated and William Verret, David Youngman,
and Shu-Teh Pan, former employees for technical assistance.
The authors also wish to thank Dr. Ronald K. Mitchum, EPA, for his sug-
gestions and review comments during the course of this study.
-------
SECTION 1
INTRODUCTION
RCRA Method 8280 as Initially proposed for the analysis of chlorinated
dibenzo-p-diox1ns and dlbenzofurans consists of four major sections: (1)
extraction of the analytes from the sample' (2) "open" column chromatographic
cleanup with alumina using a methylene chloride/hexane eluent; (3) optional
HPLC cleanup; and (4) analysis by high resolution gas chromatography/low resolu-
tion mass spectrometry (HRGC/LRMS). To test the method efficiently and to
develop appropriate modifications with minimal redundancy, each section of the
method was tested separately. Initial tests were performed on a simple sample
matrix (pottery clay soil) and on standard solutions. Only after adequate
method-performance data was collected on such materials was the analysis of
more complex samples Investigated. The first step to be elaborated was the
measurement technique. High resolution gas chromatography with mass spec-
trometry detection (HRGC/MS) and with electron capture detection (HRGC/EC) were
both tested, using guidelines from the published RCRA method. A portion of
this aspect of the study Included evaluating several types of GC columns as a
test of resolution and stability. Given the requirements of the MS detector,
the cleanup steps were then studied 1n detail and appropriate modifications
were Investigated and documented. Additional evaluation of the method involved
a systematic Investigation of the other major sections. This procedure allowed
for a separate description of each section of the method to document any recom-
mended modifications.
1
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SECTION 2
CONCLUSIONS
The major revisions which were made to the published method include: (1)
the addition of a carbon column cleanup procedure to eliminate closely related
chemical species; (2) modification 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) expansion of the extraction step so that
wet samples could be accommodated; (4) development of HPLC procedures that
could be performed reproducibly and efficiently; and (5) expansion of the 11st
of analytes to include a hepta- and the octa-chloro isomer of dibenzo-p-d1ox1n.
Performance of the revised method was investigated by precision and
accuracy determinations, by recovery of spiked analytes and 1sotop1cally-labeled
standards, and by using two Independent teams of analysts. Effects of certain
experimental parameters, such as GC column type (coating) and alumina activation
level, are also noted in this report.
After incorporating necessary revisions, satisfactory method performance
has been demonstrated on RCRA type samples. Performance of the method on
relatively complex matrices, such as sludges, still bottoms, and fly ash, has
been determined, and precision and accuracy data 1s reported. Estimates of
detection limits in these matrices are also reported.
2
-------
SECTION 3
RECOMMENDATIONS
The revised protocol has been single laboratory validated for selected
PCDD's and PCDF's in five different types of samples typical of those expected
to be analyzed under RCRA monitoring requirements. An interlaboratory comparison
test using all available PCDD and PCDF analytes in selected matrices should be
the next laboratory test of the procedure.
Expansion of the analysis to other PCDD's and PCDF's is recommended as
standards become available. Analysis of new sample matrix types will allow for
further refinement of the protocol.
3
-------
SECTION 4
EXTRACTION METHOD DEVELOPMENT AND REVISIONS
A pottery clay sample was selected as a model matrix for determining the
extraction efficiency obtained following the recommended method. A 50 ng spike
of 2,3,7,8-TCDD was added, and extraction was performed as specified in the un-
revlsed method. This experiment was performed in triplicate on cl^y and fly
ash samples as shown in Table 1. The fly ash matrix 1s discussed In more
detail in Section 9. As can be seen, even on such a simple system, extraction
performance is poor. Therefore, a modified extraction solvent system and
procedure were developed. This modified procedure adds methanol and sodium
sulfate to the petroleum ether solvent specified In the RCRA method and uses a
Kuderna-Danish concentration technique. Following these modifications, these
experiments were repeated and the results are shown in Table 2; performance
1s Improved on both dry and wet samples. As shown in the pottery city and
Missouri soil sections of this report, the revised extraction procedure resulted
in satisfactory overall method performance (e.g., dloxln-surrogate spike recovery
values) and 1s recommended for Inclusion in the revised method.
TABLE 1. PERFORMANCE OF UNREV1SED* METHOD 8280
Percent Percent Total
Recovery Recovery Calculated
Analyte Matrix Extraction** Cleanup % Recovery
2,3,7,8-TCDD
clay
44
42
18
fly ash
90
42
38
1,2,3,4-TCDD
clay
44
15
7
fly ash
90
15
14
1,2,3,4,7-PeCDD
clay
44
0
0
fly ash
90
0
0
1,2,3,4,7,8-HxCDD
clay
44
11
5
fly ash
90
11
10
2,3,7,8-TCDF
clay
44
48
21
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
fly ash
90
ii s
II
II
II
u
II
43
SSSS338SS3:
~Specific ions required for these analytes were monitored.
~~Extraction recoveries estimated for other analytes are based upon actual
recovery of 13C12-2,3,7,8-TCDD.
4
-------
TABLE 2. SOIL EXTRACTION METHOD DEVELOPMENT: RCRA METHOD
AS PUBLISHED VERSUS REVISED EXTRACTION PROCEDURE
SSSSSSSSSS3SSSSSSS8SSSSSS8SSSSSSSSSSSSSSSS5::8SSSSSSSSSSSSSSaSSSSS3SSS9S3SSSSS8
Percent Recovery of
Sample ID Weight Clay Weight Water Method Spiked 2,3,7,8-TCDD
RCRA-D1 10.0 g — 8280* 37.5%
RCRA-D2 10.0 g — 8280* 55.01
RCRA-D3 10.0 g — 8280* 38.7%
RCRA-W1 5.0 g 5.0 g 8280* ND
RCRA-W2 5.0 g 5.0 g 8280* ND
RCRA-W3 5.0 g 5.0 g 8280* ND
D-l 10.0 g — Rev. 8280** 96%
D-2 10.0 g — Rev. 8280** 72%
W-l 5.0 g 5.0 g Rev. 8280** 68%
W-2 5.0 g 5.0 g Rev. 8280** 96%
*RCRA Method 8280 was used without any drying of sample.
**Rev1sed Method 8280 as presented In this report, Appendix A.
ND s None detected; TCDD spiked at 50 ng/10 g clay; estimated detection 11m1t
75 pg.
5
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SECTION 5
DEVELOPMENT OF ALUMINA CLEANUP PROCEDURE
Experimental conditions for elution of the anaTytes from the "open"
alumina chromatographic column were determined to be crucial to method per-
formance. Using conditions as specified in the Federal Register (40 CFR 65:
14514ff, April 4, 1983), the elution profile shown in Table 3 was obtained.
This profile was unsatisfactory because many analytes of interest eluted in the
20 percent CH2Cl2/hexane fraction that was to be discarded. Furthermore, over
half of the 2,3,7,8-TCDD failed to elute, until an added step using 60 percent
CH2CI2 in hexane was performed. Changing the solvent eluent to 5 percent, 20
percent, and 60 percent CH2CI2 in hexane provided complete elution of the
2,3,7,8-TCDD, but many of the target analytes also eluted in the 20 percent
fraction, as shown in Table 4. Use of 10 percent and 60 percent CHgCl2
hexane eluent caused all analytes of interest to appear in the 60 percent
fraction, as shown in Table 5. An elution volume of 15 mL for each fraction
was consistently used.
Because use of basic materials might cause formation of chlorinated dioxins
and dibenzofurans when chlorophenols and hydroxydiphenyl ethers are present,4
it is considered preferable to use neutral alumina. Further, it would be
convenient and would eliminate a potential source of contamination if the
furnace-drying required of the basic alumina, as specified in the unrevised
method, could be avoided. Therefore, readily available Woelm Super 1 alumina
was tested. This material provided elution patterns as shown in Tables 6 and
7. Since the Woelm Super 1 alumina was more convenient to use, avoided exposure
of the sample to a basic substrate, and provided fully satisfactory elution
patterns, it was specified for use in the revised method. To demonstrate the
effect of deactivating Woelm Super 1 alumina by addition of water (via wet
solvents, wet sample, or intentional deactivation), elution profiles were
determined on Woelm Activity Grade I (1 percent added water) and with Woelm
Activity Grade II (4 percent added water). These profiles are presented in
Tables 8 and 9, respectively.
Results presented 1n Tables 3 through 9 show that the activation level of
the alumina chosen 1s crucial to satisfactory method performance for two reasons.
First, loss of a percentage of an analyte degrades the method detection limit,
and second, recoveries of different analytes are affected to quite different
extents, rendering recovery values obtained on one 1sotop1cally-labeled analyte
meaningless for another analyte.- It is also obvious that if the presence of
very small amounts of water affects elution patterns greatly, controls must be
exerted to ensure that alumina used is of reproducible and known activity level
(percent water). Note: When the revised procedure is used, the bulk of poten-
tial interferants elute in the 5 percent, 10 percent, and/or 20 percent methylene
chloride/hexane fraction in all cases.
6
-------
TABLE 3. ELUTION OF ANALYTES FROM BASIC ALUMINA
{PER UNREVISED RCRA METHOD 8280)*
Percent CH2CI2 1n Hexane (v/v)
Analyte 3% 20% 50% 60%
2,3,7,8-TCDF 52 48
1,2,3,4-TCDD 85 15
2,3,7,8-TCDD 42 58
1,2,3,4,7-PeCDD 100
1,2,3,4,7,8-HxCDD 89 11
1,2,3,4,6,7,8-HpCDD 25 75
OCDD 100
~Amount of analyte In eluate expressed In percent of total recovered from
column.
TABLE 4. ELUTION OF ANALYTES FROM BASIC ALUMINA*
Percent CH2CI2 in Hexane (v/v)
Analyte 5% 20% 60%
2,3,7,8-TCDF 9 91
1,2,3,4-TCDD 100
2,3,7,8-TCDD 100
1,2,3,4,7-PeCDD 90 10
1,2,3,4,7,8-HxCDD 58 42
1,2,3,4,6,7,8-HpCDD 8 92
OCDD 100
~Amount of analyte 1n eluate expressed In percent of total recovered from
column.
7
-------
TABLE 5. ELUTION OF ANALYTES FROM BASIC ALUMINA*
Percent CH2CI2 1n Hexane (v/v)
Analyte 10% 60%
2,3,7,8-TCDF 100
1,2,3,4-TCDD 100
2,3,7,8-TCDD 100
1,2,3,4,7-PeCDD 100
1,2,3,4,7,8-HxCDD 100
1,2,3,4,6,7,8-HpCDD 100
OCDD 100
~Amount of analyte in eluate expressed In percent of total recovered from
column.
TABLE 6. ELUTION OF ANALYTES FROM NEUTRAL ALUMINA*
(WOELM SUPER 1)
Percent CH2CI2 1n Hexane (v/v)
Analyte 5% 20% 60%
2,3,7,8-TCDF 100
1,2,3,4-TCDD 95 5
2,3,7,8-TCDD 100
1,2,3,4,7-PeCDD 94 6
1,2,3,4,7,8-HxCDD 80 20
1,2,3,4,6,7,8-HpCDD 29 71
OCDD 4 96
~Amount of analyte in eluate expressed in percent of total recovered from
column.
8
-------
TABLE 7. ELUTION OF ANALYTES FROM NEUTRAL ALUMINA
(WOELM SUPER 1)
Percent CH2CI2 1n Hexane (v/v)
Analyte 10% 60%
2,3,7,8-TCDF 100
1,2,3,4-TCDD 100
2,3,7,8-TCDD 100
1,2,3,4,7-PeCDD 100
1,2,3,4,7,8-HxCDD 100
1,2,3,4,6,7,8-HpCDD 100
OCDO 100
~Amount of analyte 1n eluate expressed 1n percent of total recovered from
column.
TABLE 8. ELUTION OF ANALYTES FROM WOELM SUPER 1
NEUTRAL ALUMINA DEACTIVATED WITH 1 PERCENT WATER*
Percent CH2CI2 1n Hexane (v/v)
Analyte 10% 60%
2,3,7,8-TCDF
2
98
1,2,3,4-TCDD
59.5
40.5
2,3,7,8-TCDO
100
1,2,3,4,7-PeCDD
64
36
1,2,3,4,7,8-HxCDD
74.5
25.5
1,2,3,4,6,7,8-HpCDD
46
54
~Amount of analyte in eluate expressed 1n percent of total recovered from
column.
9
-------
TABLE 9. ELUTION OF ANALYTES FROM WOELM SUPER 1
NEUTRAL ALUMINA DEACTIVATED WITH 4 PERCENT WATER*
Analyte
Percent CHgCl2 In
Hexane (v/v)
10%
60%
2,3,7,8-TCDF
96
4
1,2,3,4-TCDD
97.5
2.5
2,3,7,8-TCDD
85
15
1,2,3,4,7-PeCDD
97.5
2.5
1,2,3,4,7,8-HxCDD
100
1,2,3,4,6,7,8-HpCDD
99
1
~Amount of analyte 1n eluate expressed in percent of total recovered from
column.
Initial experiments were performed by preparing spiking solutions of
selected analytes (50 ng each) and applying them directly to the top of the
column. Eluates were analyzed by HRGC/EC and by HRGC/MS to determine which
eluate fractlon(s) contained the compounds spiked onto the column. These
elution experiments were performed with the analytes spiked at 50 ng each, plus
2.5 »g each of Aroclor 1016, Aroclor 1254, Aroclor 1260, pentachlorophenol,
dibenzofuran, SI 1 vex 2,4,5-T, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, and
p.p'-DDE in the spiking solution. Sample chromatograms demonstrating the
effect of this cleanup procedure are presented in Figures 1 through 3. The
bulk of the interferences elute 1n the 10 percent CHpC^/hexane fraction, as
shown 1n Figure 2. These chromatograms were obtained by HPLC/UV using methanol
solvent (Isocratic).
Note that while the elution percentages in Tables 3 through 9 represent
percent of total target analyte recovered from the column, all columns yielded
essentially quantitative recoveries.
10
-------
u.
Q
O
H
I
CO
K
CO
CM*
Q
o
O
I-
4
CO*
eg
Q
Q
U
0
Q.
1
CO*
Ol
o
O
O
x
X
•
00
%
*
CO*
01
vj
Conditions: Two 4.6 mm x25
cm octadecylsllyl columns 1n
series, 5 pm particle size.
Column and detector maintained
at 30°C. Eluted with methanol
at 1.0 ml/minute. UV detector
at 235 nm, 0.02 AUFS.
Q
O
O
o
z
«
00
K
-------
Interference mixture, 2.5 ug each:
Aroclor 1016,
Aroclor 1254,
Aroclor 1260,
Pentachlorophenol,
Dibenzofuran,
Silvex,
2,4,5-T,
2.4.5-Tri chlorophenol
2.4.6-Trichlorophenol
p,p'-DDE
101 CH2Cl2/hexane fraction from
alumina column.
30
"40
10
20
Minutes
Figure 2. HPLC analysis of analyte standard mixture
spiked with Interference mixture.
12
-------
o
0
I-
1
00
IS
CO
CM*
§§
U g
H Q.
Q ^ h
Q to *
S-"«
«
r-*
CO
ci
60% CHoC^/hexane fraction
from alumina column.
\J
O
Q
O
oo
CO
*
CM
0
Q
O
a
z
1
00
%
CO
to
ci
10
20
Minutes
"35"
~40
Figure 3. HPLC analysis of analyte standard mixture
spiked with Interference mixture.
13
-------
SECTION 6
ELABORATION OF HPLC CLEANUP PROCEDURE
Since the method as published in the Federal Register provided little
experimental detail regarding HPLC cleanup, a literature search was conducted
to identify appropriate HPLC reverse phase operating parameters for cleanup of
dioxin extracts. Two problems to be solved were: (1) to select a suitable
mobile solvent phase that would be safe to work with as well as provide adequate
separation for the compounds of interest, and (2) to find a fast but effective
procedure to concentrate the effluent fraction as obtained from the HPLC.
Acetonitrile and/or methanol singly or mixed with 5-10 percent water were
possible mobile phases. Acetonitrile possesses the drawback of a marginally
high boiling point (81.6°C). Water was also eliminated because of potential
problems at the evaporation step of the method. It was-found when working with
different solvent combinations that pure methanol performed satisfactorily as
the mobile phase and produced a retention time of 16.6 minutes for 2,3,7,8-TCDD.
Interferences commonly associated with 2,3,7,8-TCDD were also separated (Table
10 and Figures 1 through 3).
Evaporating the methanol effluent fraction using a gentle stream of pre-
purified nitrogen and a 55°C sand bath proved to be very time consuming.
Further investigation showed that concentrating this fraction to near dryness
using a 2-ball micro-Snyder column and a 90°C water bath required less than 10
minutes. This more efficient extract concentration procedure was included in
the revised method.
Initial recovery data indicated that very little loss of 2,3,7,8-TCDD
occurred during the solvent exchange into methanol prior to HPLC injection.
Recoveries of around 85 percent for 2,3,7,8-TCDD were attained for the HPLC
procedure recommended for Inclusion in the revised method. Further studies
indicated that the major source for loss of 2,3,7,8-TCDD was the transfer step.
Because the concentrator tube contained a boiling chip, the small amount of
transfer solvent used to rinse the residue from the boiling chip and the walls
of the concentrator tube was inadequate. An additional 100-yL solvent rinse
and re-1njection resulted in an additional 5 to 20 percent recovery. With the
additional rinse, the recovery of 2,3,7,8-TCDD improved to approximately 95
percent.
This HPLC procedure can be very effective 1n the cleanup of complex sam-
ples, however, additional studies have shown that the carbon column Is prefer-
able. The HPLC procedures have not been included in the final revised method
8280.
14
-------
TABLE 10. TYPICAL HPLC RETENTION TIMES OF POTENTIAL INTERFERENCES
Compound Amount (ng) Retention Time (m1n)
Pentachlorophenol
50
3.81
2,4,6-Tr1chlorophenol
50
5.80
2,4,5-Tr1chlorophenol
100
6.30
Sllvex
250
6.77
Dibenzofuran
50
8.21
p.p'-DDE
100
9.22
Aroclor 1016
100
6.91 - 9.52
Aroclor 1254
100
6.91 -10.30
Aroclor 1260
200
6.75 -15.70
2,3,7,8-TCDD
•>
II
II
II
II
II
II
II
II
m u
CM II
ii
u
ii
ii
ii
ii
ii
li
n
16.6
Conditions:
2 - 4.6-mm x 25-cm octadecylsllyl columns, 5 jim particle size.
Solvent at ambient temperature, column and detector maintained at 30°C.
Flow 1 mL/m1n methanol (172 atm). UV detector at 235 ran, 0.02 AUFS.
100 pL sample loop.
15
-------
SECTION 7
ANALYSIS OF POTTERY CLAY SAMPLES
The unrevised method 8280 specified drying the sample. However, a change
In the extraction solvent system resulted in the ability to handle wet or dry
samples of soil with good results. Thus, the sample selected for analyses can
be more representative of that collected (whether wet or dry) and the potentially
hazardous drying step can be eliminated. The new extraction procedure improved
the recovery of spiked analytes from the 37 to 55 percent range (on dry clay;
none detected on wet clay samples) for the unrevised procedure to the 68 to 96
percent level (on both dry and wet clays) for the revised procedure.
A representative sample of pottery clay containing no background inter-
ferences was spiked with suitable interferences and with analytes of interest
(PCOD's and TCDF) to determine method performance on a clean soil matrix. The
sample was homogenized and analyzed Immediately. Interferences such as Si 1 vex,
DOE, and Aroclor 1260 were used at concentrations from 10 to 200 times that of
each target analyte. Experiments were performed in duplicate by each of two
chemists (or teams of chemists) working independently. Recoveries of analytes
from pottery clay samples using the Method 8280 are summarized in Table 11,
using the HRGC/EC measurement procedure.
Performance Evaluation (PE) samples from the EPA Contract Laboratory
Program (CLP) were analyzed (blind) using the revised RCRA 8280 Method; the
results are shown in Table 12. These pottery clay samples were spiked with
nominal levels of 1 ppb TCDD and with 10 to 50 ppb levels of chlordane, DDT,
DDE, and Aroclor 1260. Acceptance windows had been determined for the analysis
of these PE samples under a CLP protocol.5 A mean concentration of 0.84 ppb
with standard deviation 18 percent was calculated for 21 sample analyses (inter-
laboratory); a 90 percent window (I.e., 90 percent of available data excluding
outliers will fall within that window) was calculated at 0.53 to 1.2 ppb. As
shown in Table 12, the data gathered by revised method 8280 using HRGC/LRMS all
fall within this acceptance window.
16
-------
TABLE 11. ANALYTE PERCENT RECOVERIES FROM POTTERY CLAY SAMPLES (HRGC/EC)*
Samples n=7
Percent
Analyte ABCDEFGY .Dev.
1,3,6.9-TCDD**
66.1
48.6
63.8
48.1
53.3
54.0
40.1
53.4
9.11
1,3,7,9-TCDD**
100.7
94.7
97.0
92.6
96.8
101.4
86.1
95.6
5.21
1,2,7,8-TCDF
86.8
90.7
94.7
94.7
99.0
96.8
95.1
94.0
4.04
1,3,7,8-TCDD
85.6
80.2
90.8
89.1
96.2
94.9
93.2
90.0
5.62
1,2,7,8-TCDD
87.8
80.8
91.9
91.8
99.1
98.7
91.8
91.7
6.29
1,2,8,9-TCDD
86.5
80.5
91.5
92.3
100.0
98.7
92.7
91.7
6.72
1,2,3,7,8-PeCDD
87.6
80.6
89.4
95.9
103.4
100.7
95.6
93.3
7.93
1,2,3,4,7-PeCDD
88.2
81.4
88.2
97.8
102.6
105.6
96.6
94.3
8.70
1,2,3,7,8-PeCDF
84.6
81.4
89.6
93.7
92.7
93.0
93.0
89.7
4.86
1,2,3,4,7,8-
HxCDF
81.7
80.0
85.4
94.2
89.9
92.9
90.5
87.8
5.51
1,2,3,4,7,8-
HxCDD
82.0
79.6
83.1
97.0
93.9
93.7
93.8
89.0
. 7.13
1.2,3,4,6,7,8-
HpCDD
72.1
77.7
81.4
105.8
96.3
84.0
99.4
88.1
12.48
OCDF
74.2
79.3
73.0
102.2
83.2
85.3
83.3
82.9
9.70
13q
2,3,7,8-TCDD
82.6
81.8
90.8
90.5
96.8
98.0
91.0
90.2
6.24
ssssassssssssssss&sssssssssssssssssssssssasasssssssassassssssssssssassssassssss
~Spikes at 50 ng each component (50 pg/uL In extract).
Analyses using revised Method 8280 procedures.
~~Tentative Isomer Identification.
17
-------
TABLE 12. ANALYSIS OF PERFORMANCE EVALUATION SAMPLES OBTAINED
FROM CONTRACT LABORATORY PROGRAM,
USING REVISED RCRA METHOD 8280
Nominal Concentration Concentration ^Cj2-2,3,7,8-TCDD
Sample ID 2,3,7,8-TCDO Found Recovery
PE-1
1 ppb
1.00 ppb
62%
PE-2
1 ppb
0.81 ppb
72%
PE-3
1 ppb
1.13 ppb
90%
PE-4
1 ppb
0.94 ppb
74%
II
II
II
II
II
II
II
It
SSS5SS9S38333SSSSSSSS833S3SS
==3============
33333S3SS3S3S838383S33:
18
-------
SECTION 8
ANALYSIS OF NATIVE MISSOURI SOIL SAMPLES
Native Missouri soil samples, environmentally contaminated with 2,3,7,8-
TCDD and interferences such as PCB's, were obtained from the Contract Laboratory
Program. These samples were thoroughly blended ("homogenized") and allquots of
20 g each were prepared and bottled. The mean TCDD concentration of this soil
reference material was determined to be 383 ppb (by an Interlaboratory study
under the EPA Contract Laboratory Program). Upon analysis of this material in
duplicate, the revised RCRA 8280 Method provided results of 370 and 377 ppb.
Allquots of this soil were spiked with other dloxln and dlbenzofuran analytes,
and percent recoveries were determined. Results of these studies are summarized
In tables of accuracy and precision data Included 1n the revised method,
Appendix A.
19
-------
SECTION 9
ANALYSIS OF FLY ASH SAMPLES
Municipal Incinerator fly ash material was obtained 1n order to provide an
environmental carbonaceous type matrix for testing. A partial, major component
characterization of this material was performed previously (see Appendix B).
This type of sample historically has required toluene or benzene extraction
with Soxhlet apparatus to remove the absorbed dioxlns and dibenzofurans. These
analytes are often found In such samples at high pot to low ppb levels.6 There-
fore, 1t was decided to spike such a sample with 13C12"2»3f7,8-TCDD and to
analyze by revised method 8280. Results of HRGC/MS analysis indicated the
presence of numerous "native" PCDD's and PCDF's 1n addition to a variety of
other compounds at higher levels. Figure 4 shows the portion of the mass
chromatograms containing the TCDD's and TCDF's in a fly ash sample. Recovery
of the carbon-13 labeled 2,3,7,8-TCOD (spiked into the sample at a concentration
of 500 pg/g) was 89 percent, using toluene/Soxhlet/revised method 8280. Esti-
mated concentrations of environmentally Incorporated dioxlns and dibenzofurans
1n the fly ash are shown 1n Tables 3 and 4 of Appendix A. Note that for this
sample, the RCRA published extraction method (toluene/Soxhlet) was used; the
revised alumina cleanup procedure was followed, and HRGC/MS was performed with
the quantitation Ions specified 1n the revised method.
20
-------
21:07 21:42 22:18 22:53
Figure 4. HRGC/MS detection of TCOO's and TCOF's In fly ash sample.
~Conditions: 10 g sample extracted and cleaned up with alumina, final volume 1 mL. Spiked with
500 pg/mL 2,3,7,8-TCDF and 500 pg/pl 13Ci2-2,3,7,8-TCDD. Chromatographed on DB-5® (J and W
Scientific, Incorporated) 170°C, 10 minutes; to 280°C at 8°/m1nute; hold 30 minutes at 280°C.
-------
SECTION 10
ANALYSIS OF CHLOROPHENOL STILL BOTTOM SAMPLES
A still bottom sample from a chlorophenol production process was obtained
from the EPA. The sample had been characterized by a Contract Laboratory,
which reported detectable concentrations of some PCDD's and PCDF's (see Table
13). Historically, these samples have been most difficult to analyze for
dioxins and dibenzofurans. Due to the presence of massive amounts of analyti-
cal interferences, poor reproducibility, low recovery of spike PCDD's and
PCDF's, and relatively poor detection limits are common.7 Nonetheless, this
challenging sample represents a sample type likely to be encountered from a
RCRA site. Full-scan HRGC/LRMS using a 30 m DB-5 column was performed for
characterization. Through this work and later MID HRGC/LRMS work with the
CP-Si 1-88 and SP-2250 columns, chlorinated phenols, diphenyl ethers, and
hydro^ydlphenyl ethers ("pre-dioxins") were found, along with the target analytes.
Apparently co-elut1on is common on all GC columns tested for dioxins, dibenzo-
furans, and d1phenyl ethers, complicating the mass spectral analysis. Careful
interpretation of spectra and retention times of standards 1s necessary to
avoid misidentifying diphenyl ethers, benzyl phenyl ethers, or hydroxyd1phenyl -
ethers having similar m/z ion clusters as target PCDD's or PCDF's.
Because of the very limited success of the revised RCRA method 8280
towards analysis of this sample, additional cleanup, using a silica Spherisorb/
PX-21 carbon column was incorporated into the cleanup procedure. This step
has been reported by Mitchum;® a similar procedure has been applied by Stalling.9
With this cleanup, good recoveries and precision were obtained as shown 1n
Tables 3 and 4 of Appendix A. The details of the carbon column cleanup are
found in Section 11.6 of the revised method.
22
-------
TABLE 13. DIRECTED ANALYSES SUMMARY: 2,4-D AND 2,4-DIBE
HERBICIDE DISTILLATION STILL BOTTOMS
Herbicide 2,4-D1chlorophenoxy Acetic Acid (2,4-D) and
2,4-D Isobutyl Ester (2,4-D-IBE)
Samp! e
Waste Stream No.
Sample Codes
Description
111
ARB 12-14-04
Distillation Bottoms (tar) from DCP
production
Directed Analyses
Polychlorod1benzod1ox1ns, jigA (kg)
2,3,7,8-TCDD
Tetrachloro* s
Pentachloro's
Hexachloro's
Heptachloro's
Octachloro's
Polychlorodlbenzofurans, pg/L (kg)
2,3,7,8-TCDF
Tetrachloro's
Pentachloro's
Hexachloro's
Heptachloro's
Octachloro's
529 Mg/kg (1)
2,300
14,000
3,700
26,000 iig/kg
96,000
350,000
590
190
6
Surrogates: (
recovery)
(percent
2,3,7,8-TCDD-13C12
Semivolatlles, mg/L (kg)
Phenol
2-Chlorophenol
2,6-Dichlorophenol
2,4-D1chlorophenol
2,4,6-T r1chlorophenol
2,4,5-Tr1chlorophenol
2,6-D
2,4-D
2,4-D-IBE
Surrogates, percent recovery
Phenol-d5
Naphthalene-ds
9-Phenylanthracene
NA - Not analyzed (1) Concentration level 1s for two tetrachlorodlbenzo-p-
dloxln Isomers, one of which Is the 2,3,7,8-TCDD Isomer.
Not detected.
95%
2,900 mg/kg
NA
18,000
145,000
NA
NA
NA
100.4%
Not added
85.2
23
-------
SECTION 11
ANALYSIS OF SLUDGE SAW>LES
A sludge sample was obtained from the EPA. The sludge represents a sample
from a cooling tower that receives both creosote and pentachlorophenollc waste-
waters. This sample contained a high percentage of water (761) and rivaled the
chlorophenol still bottom sample 1n complexity of the organic components. The
water was removed by azeotroplc distillation with toluene and the toluene
extract was used for analysis of the PCDD's and PCDF's present. This extract
was cleaned up using the revised RCRA Method 8280 procedure. This procedure
included the use of a silica Spher1sorb/PX-2l carbon column. The mass chromato
grams before and after the silica Spherisorb/PX-21 charcoal column cleanup are
shown 1n Figures 5 and 6. The major interferences elute 1n the same region as
the TCDD's and TCDF's and are greatly reduced by the silica Spher1sorb/PX-2l
procedure. Recoveries and precision obtained are shown 1n Tables 3 and 4 in
the revised method, Appendix A.
24
-------
100.0
TCDD's
RIC
ro
<71
PeCDD's
PeCDF's HxCDD's
HxCOF's
2000
23:28
ifti
2500
29:20
HpCDD's
HpCDF's
300o"
35:12
OCDD's
OCDF's
3500 Scan
41:04 Time
Figure 5. Mass chromatogram of sludge sample prior to silica
Spherlsorb/PX-21 charcoal column cleanup.
Conditions: 30 m DB-5® column (J and W Scientific, Incorporated), 170"C, 10 minutes:' 170°C to 280'C
at 8 /minute; hold 30 minutes at 280°C.
-------
100.0-1
TCDD's
TCDF's
n PCDD's
PCDF's
RIC-
ro
a\
(|J
O W
-P
- n.
V> N
w y»
* >¦
H *
8 g
° §.
2000
23:28
HxCDD's
HxCDF's
HpCDD's
HpCDF's
OCDD's
OCDF's
2500
29:20
3000
35:12
3500
41:04
Scan
Time
Figure 6. Mass chromatogram of sludge samples after silica
Spher1sorb/PX-2l charcoal column cleanup.
Conditions: 30 m DB-5® column {J and W Scientific, Incorporated), 170°C, 10 minutes; 170°C to 280°C at
8"/minute; hold 30 minutes at 280°C. Carbon-13 standards at 500 pg/pL.
-------
SECTION 12
RATIONALE FOR PROPOSED METHOD MODIFICATIONS
The RCRA method with revisions was subjected to performance tests including
(1) analysis of reference materials containing 2,3,7,8-TCDD and interferences
and (2) precision and accuracy determinations on samples having known composi-
tion obtained by spiking the sample matrix. The revised method is provided in
Appendix A. Rationale for each change in the method as published In the Federal
Register, April 4, 1983, 1s presented below, section by section:
4.3.2 Fused silica capillary columns are recommended as being chromato-
graphically equivalent to glass and easier to work with; furthermore, they can
be threaded directly Into the mass spectrometer source for improved sensitivity
of detection. As shown in Table 1 of the revised method, four columns were
evaluated using a commercially available mixture containing 1,2,3,4-TCDD,
1,2,3,4,7-PeCDD, 1,2,3,4,7,8-HxCDD, and 1,2,3,4,6,7,8-HpCDD and 2,3,7,8-TCDF.
Retention times greater than about 40 to 50 minutes were considered Impractical
although some analytes were measured at greater retention times for comparison
purposes. Both CP-Si 1-88 and SP-2250 gave reasonable separation of 2,3,7,8-TCDD
from the other TCDD's tested. Separations of 2,3,7,8-TCDD from the closest
eluting isomer using the EPA Contract Laboratory Program GC Column Performance
Check Mixture (containing seven TCDDs) were as follows: 21 percent valley on 30
m SP-2250; 16 percent valley on 50 m CP-Si 1-88; 30 percent valley on 30 m
DB-225; 64 percent valley on 30 m DB-5 column. Hence, separation of 2,3,7,8-TCDD
from other TCDD's was best on CP-Si 1-88 and poorest on 30 m DB-5. However,
separation on all four columns was adequate to observe whether any close-elutlng
isomers (to 2,3,7,8-TCDD) were present in a given sample. Column cost 1s
approximately proportional to length, and nonbonded phases are less durable
than bonded phases such as DB-5 or DB-225. On some types of interferences,
less polar columns such as DB-5 may give better separation of Interferences
from the analytes of interest (PCDD's and PCDF's). Temperature programs deve-
loped by this laboratory with each type of GC column are shown in Table 1.
4.3.3 The MS system should be capable of monitoring eight ions simul-
taneously (see Section 10.4). Sensitivity of quadrupole low-resolution systems
is consistent with the revised specification of 5:1 signal to noise on 0.15 ng
of native TCDD; the original specification of .015 ng of ^'Cl^TCDD Is beyond
the sensitivity capabilities of many systems, particularly in EI mode and on a
routine basis. Monitoring M/z 320 (or 322) is correct for native TCDD; 328
would be correct for 3 CI4-TCDD..
4.3.4 Directly Interfacing the column into the MS source 1s preferable
and consistent with other EPA activities relating to dioxin analysis.
27
-------
4.19
The added carbon column 1s described.
5.1 Two percent 1s a typographical error; 20 percent 1s correct.
5.3 Chemicals added reflect experience of dloxln analytical labora-
tories that isooctane and toluene can be suitable replacements for tridecane
(or tetradecane) and benzene, respectively. 6,7
5.5 Per experience of this laboratory, as discussed In Section 5 of
this report, Woelm Super 1 alumina is specified 1n the revised method.
6.1 Elutlon patterns/retention times on "open" alumina columns and
carbon columns should be verified. It 1s a worthwhile quality assurance measure
to check the 8 percent methylene chloride/hexane fraction to ensure no analytes
are lost 1n that fraction.
6.2 Use of ^c^-TCDD labeled standards as stated is due to availability
and cost.
6.3 Again, the isotopic label 1s changed to carbon. This change
reflects availability and cost of these labeled PCDD and PCOF standards. Use
of 0.15 ng native TCDD, monitored at m/z 320, reflects reasonable sensitivity
requirements for quadrupole GC/MS systems. It 1s considered worthwhile to
check GC column performance daily, because most columns that have been used for
these types of analytes are subject to rapid performance degradation. Analyses
conducted under the EPA-CLP have demonstrated this problem, even on relatively
simple soil samples.
7.2 For some matrices/samples of Interest, precision and accuracy will
not be known in advance, so "determine" is more appropriate than "validate."
Incorporation of field blanks Into the quality assurance "package" 1s a
standard procedure.
8.2 The sentence on sample preservation 1s removed. Preservation Is
generally considered unnecessary for these types of samples because the analytes
are exceptionally stable.
9.0 Procedures are added for representative samples. The revised
extraction procedure eliminates the need for drying the sample. Thus, a more
representative aliquot of the total sample may be analyzed and analysis time 1s
reduced. Oust and sample handling are reduced. Samples may be dried if analyti-
cal results based on dry sample weight are desired.
9.7 through 9.8 Method performance data are Included in this report for the
Method 8280 specified Woelm basic alumina and for the revised procedure's Woelm
Super 1 neutral alumina. The Super 1 alumina avoids exposure of the sample to
basic material, performs at least as well as the basic alumina on the separation
of interferences, and requires no activation step {and concomitant possibility
of contamination).
9.9 The added procedures for the carbon column cleanup are described.
28
-------
10.3.3 This requirement Is considered essential.*0 Dlphenylether Inter-
ferences are known to coelute with dlbenzofuran analytes, the ethers fragment
1n the mass spectrometer to yield (M-C12)+ Ions with the same exact masses as
chlorinated dlbenzofurans. Differentiation with GC/MS analysis Is, therefore,
possible only from retention time and by monitoring the chlorinated dlphenylether
molecular 1on m/z value.
10.4 For proper quality assurance, use of the monitoring Ions shown 1n
this section 1s Important. This decision 1s consistent with other EPA dloxln
monitoring efforts.
10.5 Another technique that has been shown (under EPA Special Analytical
Services CLP efforts) to provide satisfactory results when Interferences are
present Is HRGC/MS/MS. This technique could be Included as an alternate measure-
ment technique.
11.1 Quantitation 1s based on the internal standard added to the sample
before extraction.
29
-------
REFERENCES
1. Federal Register 40 CFR 261: 1978, January 14, 1985.
2. Federal Register 40 CFR 65: 14514, April 4, 1983.
3. Test Methods for Evaluating Solid Waste—Physical/Chenrlcal Methods, G.P.O.
Stock No. 055-002-81001-2. Gray, A., D1p1nto, V., and Solomon, I. J. Org.
J. Chem. 41, 2428 (1976). Gray, A., Cepa, S., Solomon, I., and Aniline, 0.
Org. ChemT41, 2435 (1976).
4. Morlta, M., Nakagawa, J., and Aklyama, K. Bull. Environ. Contam. Toxicol.
18, 200 (1977). Nestrlck, T., Lamparski, L., and Stehl, R. Anal. Chem.
5T, 2273 (1979). Lamparski, L., and Nestrlck, T. Chemospher 10, 3 (1981).
5. U. S. Environmental Protection Agency, Procurement Section A. Chenrlcal
Analytical Services for 2,3,7,8-Tetrachlorod1benzo-p-diox1n, Invitation
for Bid Solicitation Number MA 84-A002, December 9, 1983.
6. Olie, K., Verneulen, P., and Hutzlnger, 0. Chemospher 6, 455 (1977).
Eiceman, G., Clement, R., and Karasek, F. Anal. Chem. 31, 2343 (1979).
Elceman, G., Vlau, A., and Karasek, F. Anal. Chem. 52.T492 (1980).
Lustenhouwer, J., Olie, K., and Hutzlnger, 0. Chemospher 9, 501 (1980).
Kooke, R., Lustenhouwer, J., 011e, K., and Hutzlnger, 0. Tfnal. Chem. 53
461 (1981). Eiceman, G., Clement, R., and Karasek, F. Anal. Chem. 53"T55
(1981). Nestrlck, T., Lamparski, L., Crummett, W., and Shadoff, L.
Anal. Chem. 54. 824 (1982). Karasek, F., Clement, R., and Viau, A.
J. Chromatogr. 239, 173 (1982).
7. Harless, R. L. U.S. Environmental Protection Agency, EMSL-RTP, N.C.,
personal communication. Jensen, S., and Renberg, L. Amblo 1, 62 (1972).
Tulp, M., and Hutzlnger, 0. Blomed. Mass Spectrom. 5, 224 (T978).
Shadoff, L.t Blaser, W., Kocher, C., and Fravel, H. "Anal. Chem. 50,
1586 (1978). Phlllipson, D., and Puma, B. Anal. Chem. 52, 2328 TT980).
8. Korfmacher, W., Rushing, L., Nestorlck, D., Thompson, H., Mitchum, R.,
and Kominsky, J. J. High Resol. Chrom. and Chrom. Commun. 8, 12 (1985).
9. Smith, L., Stalling, D., and Johnson, J. Anal. Chem. 56, 1830 (1984).
10. Harless, R. Analysis for Tectrachlorodlbenzofurans. In: Thirty-first
Annual Conference of Mass Spectrometry and Allied Topics, American Society
for Mass Spectrometry, Boston, Massachusetts, 1983. p. 221.
30
-------
APPENDIX A
RCRA METHOD 8280 WITH REVISIONS BASED ON SINGLE-LABORATORY TESTING:
METHOD OF ANALYSIS FOR CHLORINATED DIBENZO-P-DIOXINS
AND DIBENZOFURANS
Method 8280
1. Scope and Application
^This method 1s appropriate for the analysis of tetra-, penta-, hexa, hepta-,
and octachlorlnated d1benzo-£-diox1ns and dibenzofurans.
^Analytical protocol for determination of TCDD's 1n phenolic chemical wastes
and soil samples obtained from the proximity of chemical dumps. T. 0. Tlernan
and M. Taylor. Brehm Laboratory. Wright State University. Dayton, Ohio
45435.
Analytical protocol for determination for chlorinated d1benzo-£-diox1ns and
chlorinated dibenzofurans 1n river water. T. 0. Tlernan and M. laylor. Brehm
Laboratory. Wright State University. Dayton, Ohio 45435.
1.1 This method allows for the determination of chlorinated dibenzo-p-
dloxins and chlorinated dibenzofurans 1n chemical wastes including still bottoms,
filter aids, sludges, spent carbon, reactor residues, and 1n soils.
1.2 The sensitivity of this method 1s dependent upon the level of
Interferences.
1.3 This method is recommended for use only by analysts experienced with
residue analysis and skilled in mass spectral analytical techniques.
1.4 Because of the extreme toxicity of these compounds, the analyst must
take necessary precautions to prevent exposure to himself, or to others, of
materials known or believed to contain PCDD's or PCDF's. Typical infectious
waste Incinerators are probably not satisfactory devices for disposal of materials
highly contaminated with PCDD's or PCDF's. Generators of 1 Kg or more of dloxin
wastes must register as a generator. A laboratory planning to use these compounds
should prepare a disposal plan to be reviewed and approved by EPA's Dloxin Task
Force (Contact Conrad Kleveno, WH-548A, U.S. EPA, 401 M Street S.W., Washington,
D.C. 20450). Additional safety Instructions are outlined 1n EPA Test Method
613.
2. Summary of the Method
31
-------
2.1 This method is an extraction, cleanup procedure and high resolution
capillary column gas chromatography-low resolution mass spectrometry method,
using and Internal standard techniques, which allow for the measurement of
PCDD's and PCDF's 1n the extract.
2.2 If Interferences are encountered, the method provides selected general
purpose cleanup procedures to aid the analyst In their elimination. The analysis
flow chart, 1s shown in Figure 1.
3. Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of chromatographic data. All of these materials must be demonstrated to
be free from Interferences under the conditions of the analysis by running
method blanks. Solvents distilled 1n all-glass systems are required.
3.2 Interferences co-extracted from the samples will vary considerably
from source to source, depending upon the industrial process being sampled.
PCDDs and PCDFs are often associated with other interfering chlorinated com-
pounds such as PCB's and polychlorlnated dlphenyl ethers which may be at con-
centrations several orders of magnitude higher than that of the analytes of
interest. Retention times of analytes must be verified using standards. While
general cleanup techniques are provided as part of this method, unique samples
may require additional cleanup approaches such as HPLC, to achieve the detec-
tion levels stated in Table 6.
3.3 Resolution of the 2,3,7,8-TCDD Isomer from other closely elutlng TCDDs
1s used to establish column performance criteria. High resolution capillary
columns are used to resolve as many PCDD and PCDF Isomers as possible; however,
no single column 1s known to resolve all of the Isomers in a complex mixture.
4. Apparatus and Materials
4.1 Sampling equipment for discrete or composite sampling.
4.1.1 Grab sample bottle—amber glass, 1-I1ter or 1-quart volume. French or
Boston Round design 1s recommended. The container must be washed and solvent
rinsed before use to minimize Interferences.
4.1.2 Bottle caps—threaded to screw onto the sample bottles. Caps must be
lined with Teflon. Solvent washed foil, used with the shiny side toward the
sample, may be substituted for the Teflon If the sample 1s not corrosive.
4.1.3 Compositing equipment—automatic or manual compositing system. No
tygon or rubber tubing may be used, and the system must Incorporate glass
sample containers for the collection of a minimum of 250 mL. Sample containers
must be kept refrigerated after sampling.
4.2 Water bath—heated, with concentric ring cover, capable of temperature
control (+2#C). The bath should be used in a hood.
32
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Sample
Add ^Cj2-2,3,7,8-TCDD (Internal Standard)
Extract as Section 9.2
(1)
(2)
(3)
(4)
(5)
(6)
(7)
V
Figure 1. Revised Method 8280 analysis flow chart.
(1)
(2)
V
Sample
Extract
Wash with 20% KOH
Wash with H2O
Wash with conc. H2SO4
Wash with water
Dry extract
Evaporate to dryness and
redlssolve 1n hexane
Alumina column
33
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4.3 Gas chromatograph/mass spectrometer data system.
4.3.1 Gas chromatograph: An analytical system with a temperature-
programmable gas chromatograph and all required accessories including syringes,
analytical columns, and gases.
4.3.2 Fused silica capillary columns are required. As shown 1n Table 1,
four columns were evaluated using a column performance check mixture containing
1,2,3,4-TCDD, 1,2,3,4,7-PeCDD, 1,2,3,4,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, and
2,3,7,8-TCDF.
The columns Include the following: (a) 50 m CP-S11-88 programmed 60°-190° at
20°/minute, then 190°-240° at 5°/minute; (b) 30 m DB-5 programmed 170° for 10
minutes, then 170°-280° at 8°/m1nute, hold at 280°C for 30 minutes; (c) 30 m
SP-2250 programmed 70°-320° at 10°/minute. Column/conditions (a) provide good
separation of 2,3,7,8-TCDD from the other TCDD's at the expense of longer
retention times for higher homologs. Column/conditions (b) and (c) provide
separation of 2,3,7,8-TCDD. Resolution of 2,3,7,8-TCOD from the other
TCDD's 1s better on column (c), but column (b) is more rugged, and may provide
better separation from certain classes of Interferants.
4.3.3 Mass spectrometer: Capable of scanning from 45 to 450 amu every 1
second or less, utilizing 70 volts (nominal) electron energy In the electron
Impact Ionization mode and producing a mass spectrum which meets all the criteria
1n Table 2 when 50 ng of decafluorotrlphenylphosphlne (DFTPP) 1s Injected
through the GC Inlet. The system must also be capable of selected 1on monitoring
(SIM) for at least 8 1ons simultaneously, with a cycle time of 1 sec or less.
Minimum Integration time for SIM is 50 ms. Selected 1on monitoring 1s verified
by injecting 0.15 ng of native TCDD to give a minimum signal-to-noise ratio of
5 to 1 at mass 320.
4.3.4 GC/MS interface: Any GC-to-MS interface that gives acceptable cali-
bration points for each compound of interest at concentration monitored and
achieves acceptable tuning performance criteria (see Sections 6.1-6.3) may be
used. GC-to-MS Interfaces constructed of all glass or glass-lined materials
are recommended. Glass can be deactivated by silanizlng with dichlorodimethyl-
sllane. Inserting a fused silica column directly Into the MS source 1s
recommended.
4.3.5 Data system: A computer system must be Interfaced to the mass spectrom-
eter. The system must allow the continuous acquisition and storage on machine-
readable media of all mass spectra obtained throughout the duration of the
chromatographic program. The computer must have software that can search any
GC/MS data file for ions of a specific mass and that can plot such Ion abundances
versus time or scan number. This type of plot 1s defined as an Extracted Ion
Current Profile (EICP). Software must also be able to Integrate the abundance,
in any EICP, between specified time or scan number limits.
4.3.6 High Performance Liquid Chromatography: HPLC pump with loop valve
Injector.
34
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4.4 Apparatus Pipettes-Disposable, Pasteur, 150 mm long x 5 mm ID (Fisher
Scientific Company, No. 13-678-6A or equivalent).
4.5 Amber glass bottle (500 mL, Teflon-lined screw cap).
4.6 Reacti-v1al 1 ml, amber glass (silanized) (Pierce Chemical Company).
4.7 500 mL Erlenmeyer flask (American Scientific Products cat No. f4295-
500f0) fitted with Teflon stoppers (ASP No. S9058-8 or equivalent).
4.8 Wrist Action Shaker (VWR No. 57040-049 or equivalent).
4.9 125 mL and 2 L Separatory Funnels (Fisher (10-437-5b or equivalent).
4.10 500 mL Kuderna-Danish fitted with a 10 mL concentrator tube and
3-ball Snyder column (Ace Glass No. 6707-02, 6707-12, 6575-02 or equivalent).
4.11 Teflon boiling chips (Berghof American No. 15021-450 or equivalent).
Wash with hexane prior to use.
4.12 300 mm x 10.5 mm glass chromatographic column fitted with Teflon stop-
cock.
4.13 15 mL conical concentrator tubes (Kontes No. K-288250 or equivalent).
4.14 Adaptors for concentrator tubes (14/20 to 19/22) (Ace Glass No. 9092-20
or equivalent).
4.15 2-Ball mlcro-Snyder columns (Ace Glass No. 6709-24 or equivalent).
4.16 Nitrogen evaporator (N-Evap No. 1156 or equivalent). Teflon tubing
connection to trap and gas regulator 1s required.
4.17 Microflex conical vials (Kontes K-749000 or equivalent).
4.18 Filter paper (Whatman No.54 or equivalent).
4.19 Carbon Column: An HPLC column (4.6 mm x 7 cm, stainless steel),
prepared by mixing 5 percent (by weight) active carbon PX-21 (Amoco Research
Corporation, Chicago, Illinois, or the equivalent active carbon AX-21, washed
with methanol and dried in vacuo at 110#C, Anderson Development Co., Adrian,
Michigan) and 10 pm silica (Spherlsorb S 10 W from Phase Separations, Inc.,
Norwalk, Connecticut). The material must be stirred and sieved through a 40 um
screen to remove any clumps.4/
4.20 Dean-Stark trap, 10 mL with T joints, condenser and 125 mL flask.
4/ The carbon column preparation and use 1s adapted from W. A. Korfmacher,
L. G. Rushing, D. M. Nestorick, H. C. Thompson, Jr., R. K. Mitchum,
and J. R. Kominsky, Journal of High Resolution Chromatography and
Chromatography Communications, 8, 12-19 (1985).
35
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5.
Reagents
5.1 Potassium hydroxide-(ACS), 20 percent (w/v) 1n distilled water.
5.2 Sulfuric acid-(ACS), concentrated.
5.3 Methylene chloride, hexane, benzene, petroleum ether, methanol, tet-
radecane, Isooctane, toluene. Distilled 1n glass.
5.4 Prepare stock standards 1n a glovebox from concentrates or neat
materials. The stock solutions are stored in the dark at 4°C, and checked
frequently for signs of degradation or evaporation, especially just prior to
the preparation of working standards.
5.5 Alumina, neutral, Super 1, Woelm, 80/200 mesh. Store at room tempera-
ture 1n a desiccator with CaS04 drying agent. Oven drying at 600°C overnight
1s acceptable, but alumina so processed should be checked for contamination by
solvent rinsing and GC/ECD analysis.
5.5 Prepurlfied nitrogen gas.
5.7 Anhydrous sodium sulfate (reagent grade). Extracted overnight with
hexane using a Soxhlet extraction apparatus and dried at 100°C.
6. Calibration
6.1 Before using any cleanup procedure, the analyst must process a series
of calibration standards through the procedure to validate elutlon patterns and
the absence of interferences from reagents. Both open column and carbon column
performance must be checked. Routinely check the 8 percent C^C^/hexane eluate
of environmental.extracts from the alumina column for presence of target analytes.
6.2 Prepare multi-level calibration standards keeping the recovery stan-
dard (13C12-1,2,3,4-TCDD) and the Internal standard 5/ ("Cjo-Z.S.y.S-TCDD)
at fixed concentrations of 500 ng/mL. Recommended concentration levels for
standard analytes are 200, 500, 1000, 2000, and 5000 ng/mL. Calculation of
response factors 1s described In Section 11.1. Standards must be analyzed
using the same solvent as used 1n the final extract, toluene is recommended.
A wider calibration range 1s useful provided it can be described within the
linear range of the method.
5/ ^c^-iabeled TCDD Is available from Cambridge Isotope Laboratory,
Woburn, Massachusetts. Proper standardization requires the use of a
specific labeled Isomer for each congener to be determined. When
labeled PCDD's and PCDF's of each homolog are available, their use
will be required consistent with the technique of isotoplc dilution
mass spectral analysis.
36
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6.3 Establish operating parameters for the GC/MS system as indicated in
Section 10.1 of this method. The Instrument should be tuned as described in
Table 2 by the use of decafluorotriphenyl phosphine (DFTPP). By injecting
calibration standards, establish the standard response factors vs. Cio-
2,3,7,8-TCDD (PCDF response factors are established, vs. "Cjo-TCDF if this
standard 1s used). An adequate detection limit should be verified by Injecting
0.15 ng of 13Ci2-2,3,7,8-TCDD which should give a minimum signal to a noise
ratio of 5 to I at mass 330. GC column performance should be checked for
resolution and peak shape dally using a mixed standard such as the GC column
performance check mixture described in Section 4.3.2.
7. Quality Control
7.1 Before processing any samples, the analyst should demonstrate through
the analysis of a distilled water method blank that all glassware and reagents
are Interference-free, Each time a set of samples 1s extracted, or there is a
change 1n reagents, a method blank shall be processed as a safeguard against
laboratory contamination.
7.2 Standard quality assurance practices must be used with this method.
Field replicates must be collected to validate the precision of the sampling
technique. Laboratory replicates must be analyzed to determine the precision
of the analysis. Fortified samples must be analyzed to establish the accuracy
of the analysis. Field blanks must be collected to verify that sample collec-
tion processes are free from cross-contamlnation.
8. Sample Collection, Preservation, and Handling
8.1 Grab and composite samples must be collected In glass containers.
Conventional sampling practices should be followed. The bottle must not be
prewashed with sample before collection. Composite samples should be collected
1n glass containers. Sampling equipment must be free of tygon, rubber tubing
and other potential sources of contamination.
8.2 All samples must be stored at 4°C, extracted within 7 days and completely
analyzed within 30 days of collection.
9. Extraction and Cleanup Procedures
9.1 Internal standard addition. Use an aliquot of 0.1-10 g sample (typical
sample size requirements for each type of matrix is provided in Section 9.2) of
the chemical waste or soil to be analyzed. Transfer the sample to a tared
flask and determine the weight of the sample. Add an appropriate quantity of
Ci2-2»3,7,8-TCDD, which 1s employed as an internal standard. All samples
should be spiked with the internal standard, ^C^-Z.SJ.S-TCDD, to give an
approximate concentration of 500 pg/mL 1n the final concentrated extract. As
an example, a 10 g sample concentrated to a final volume of 100 uL requires the
addition of 50 ng of 13C^2"2,3,7,8-TCDD, at 100% recovery.
9.2 Extraction
9.2.1 Sludge. Extract the sludge samples by refluxing a 2 g sample with
37
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50 mL of toluene 1n a 125 mL flask fitted with a Dean-Stark water separator.
Continue refluxlng the sample until all the water has been removed. Cool the
sample, filter the toluene solution through Whatman No. 54 filter paper (or
equivalent) Into a 100 mL round bottom flask. Concentrate the extract to just
dryness using a rotary evaporator at 50°C. Proceed with step 9.2.4.
9.2.2 Still bottom. Extract the still bottom sample by mixing 100 mg of
sample with 10 mL of toluene and filtering the solution through Whatman No. 54
filter paper (or equivalent) Into a 50 mL round bottom flask. Rinse the filter
with 5 mL of toluene. Concentrate the combined toluene solution to just dry-
ness using a rotary evaporator at 50°C. Proceed with step 9.2.4.
9.2.3 Fly ash. Extract the fly ash sample by placing 10 g of sample and
10 g of anhydrous sodium sulfate 1n a Soxhlet extraction apparatus charged with
toluene and extract for 16 hours using a three cycle/hour schedule. Cool and
filter the toluene extract through Whatman No. 54 filter paper (or equivalent)
into a 500 mL round bottom flask. Rinse the filter with 5 mL of toluene.. Con-
centrate the combined toluene solution just to dryness using a rotary evapo-
rator at 50°C. Proceed with step 9.2.4.
9.2.4 Transfer the residue to a 125 mL separatory funnel using 15 mL of
hexane. Rinse the flask with 2-5 mL allquots of hexane and add the rinses
to the funnel. Shake 2 minutes with 50 mL of 5% NaCl solution, discard the
aqueous layer and proceed with step 9.3.
9.2.5 Soil. Extract soil samples by placing 10 grams of sample and 10 grams
of anydrous sodium sulfate in a 500 mL Erlenmeyer flask fitted with a Teflon
stopper. Add 70 mL of petroleum ether and 30 mL for methanol, 1n that order,
to the Erlenmeyer flask. Shake on a wrist-action shaker for two hours. The
solid portion of sample should mix freely. If a smaller soil aliquot is used,
scale down the amount of methanol proportionally.
9.2.5.1 Filter the extract from Section 9.2.5 through a glass funnel fitted
with filter paper (Whatman No. 54 or equivalent) and filled with anhydrous
sodium sulfate Into a 500 mL Kuderna-Danish (KD) concentrator fitted with a
10 mL concentrator tube. Add 50 mL of petroleum ether to the Erlenmeyer
flask, restopper the flask and swirl the sample gently, remove the stopper
carefully and decant the solvent through the funnel as above. Wash the sodium
sulfate on the funnel with two 5 mL portions of petroleum ether.
9.2.5.2 Add a Teflon boiling chip and a three-ball Snyder column to the KD
flask. Concentrate 1n a 70°C steam bath to an apparent volume of 10 mL.
Remove the apparatus from the steam bath and allow 1t to cool for 5 minutes.
9.2.5.3 Add 50 mL of hexane and a new boiling chip to the KD flask. Concen-
trate 1n a steam bath to an apparent volume of 10 mL. Remove the apparatus
from the steam bath and allow to cool for 5 minutes.
9.2.5.4 Remove and invert the Snyder column and rinse it down Into the KD with
two, 1 mL portions of hexane. Decant the contents of the KD and concentrator
tube Into a 125 mL separatory funnel. Rinse the KD with two additional five mL
portions of hexane, combine. Proceed with step 9.3.
38
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9.2.6 Aqueous samples. Mark the water meniscus on the side of the 1-L sample
bottle for later determination of the exact sample volume. Pour the entire
sample (approximately 1 L) into a 2-L separatory funnel. Note: A continuous
liquid-liquid extractor may be used in place of a separatory funnel.
9.2.6.1 Add 60 mL methlylene chloride to the sample bottle, seal and shake 30
seconds to rinse the inner surface. Transfer the solvent to the separatory
funnel and extract the sample by shaking the funnel for 2 minutes with periodic
venting. Allow the organic layer to separate from the water phase for a minimum
of 10 minutes. If the emulsion interface beteen layers 1s more than one-third
the volume of the solvent layer, the analyst must employ mechanical techniques
to complete the phase separation. Collect the methylene chloride (3 x 60 mL)
directly into a 500 mL Kuderna-Danlsh concentrator (mounted with a 10 mL
concentrator tube) by passing the sample extracts through a filter funnel packed
with a glass wool plug and 5 g of anhydrous sodium sulfate. After the third
extraction, rinse the sodium sulfate with an additional 30 mL of methylene
chloride to ensure quantitative transfer.
9.2.6.2 Attach a Snyder column and concentrate the extract until the apparent
volume of the liquid reaches 5 mL. Remove the K-D apparatus and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column, add 50 mL
hexane, reattach the Snyder column and concentrate to approximately 5 mL.
Rinse the flask and the lower joint with 2 x 5 mL hexane and combine rinses
with extract to give a final volume of about 15 mL.
9.2.6.3 Determine the original sample volume by refilling the sample bottle to
the mark and transferring the liquid to a 1000-mL graduated cylinder. Record
the sample volume to the nearest 5 mL. Proceed with Step 9.3
9.3 Partition the solvent against 40 mL of 20 percent (w/w) potassium hydrox-
ide. Agitate for two minutes. Remove and discard the aqueous layer (bottom).
9.4 Partition the solvent against 40 mL of distilled water. Agitate for
two minutes. Remove and discard aqueous layer (bottom).
9.5 Partition the solvent against 40 mL of concentrated sulfuric acid.
Agitate for two minutes. Remove and discard the aqueous layer (bottom). Repeat
the acid washings until no color 1s visible in the acid layer.
9.6 Partition the extract against 40 mL of distilled water. Agitate for
two minutes. Remove and discard aqueous layer (bottom). Dry the organic layer
by pouring through a funnel containing anhydrous sodium sulfate, wash with two
5 mL portions of hexane, and concentrate the hexane solution to near dryness
with a rotary evaporator (35°C water bath).
9.7 Pack a gravity column (glass 300mm x 10.5mm), fitted with a Teflon
stopcock, 1n the following manner:
Insert a glass-wool plug Into the bottom of the column. Add a 4 gram layer of
sodium sulfate. Add a 3.6 gram layer of Woelm super 1 neutral alumina. Tap
the top of the column gently. Vloelm super 1 neutral alumina need not be activated
or cleaned prior to use but should be stored and sealed 1n a desiccator. Add a
39
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4 gram layer of sodium sulfate. Elute with 20 mL of hexane and close the stop-
cock just prior to the exposure of the sodium sulfate layer to air. Discard
the effluent. Check the column for channeling. If channeling is present dis-
card the column. Do not tap on a wetted column.
9.8 Dissolve the residue from 9.6 1n 2 mL of hexane and apply the hexane
solution of the sample to the top of the column. Elute with enough hexane to
transfer the sample cleanly to the surface of the alumina. Discard the effluent.
9.8.1 Elute with 10 mL of 8 percent methylene chloride by volume 1n hexane.
Check that no PCDD's or PCDF's eluted in this fraction as a quality assurance
step.
9.8.2 Elute the PCDD's and PCDF's from the column with 15 mL of 60 percent
(v/v) methylene chloride 1n hexane and collect this fraction in a conical
shaped (15 mL) concentrator tube.
9.9 Carbon column cleanup.
9.9.1 Using N2, gently concentrate both fractions from the alumina column
(Section 9.8) to about 1 mL. Wash the sides of the tube with a small volume
(100-300 pL) of hexane and reconcentrate to about 1 mL. Save the 8 percent
fraction for GC/MS injection to check for any bleedthrough of PCDD's and PCDF's
(a quality assurance step). Evaporate the 60 percent CH2Cl2/hexane fraction to
about 400 uL and prepare for transfer to a HPLC Injector loop (1.0 mL) for
carbon column cleanup. Rinse the centrifuge tube with 500 uL hexane, and add
both fractions to HPLC injector loop.
9.9.2 Elute the column at 2 mL/minute, ambient temperature, with 30 mL of
cyclohexane/methylene chloride 1:1 (v/v). Discard effluent. Next elute the
column with 10 mL of C^Clp/MeOH/Benzene 70:20:5 (v/v). Discard effluent.
Backflush the column with 40 mL toluene to elute and collect PCDD's and PCDF's
(entire fraction). The column 1s cleaned by pumping an additional 30 mL
methanol followed by 40 mL of toluene In the back flush position. After
returning the column to the original position, 30 mL of cyclohexane/methylene
chloride 1:1 (v/v) 1s pumped through the column to reequlHbriate 11 In prepa-
ration for the next sample. The column must be checked for bleed following
the analysis of high level samples (>500 ppb) and replaced as needed.
9.9.3 Evaporate the toluene fraction to about 1 mL on a rotary evaporator
using a water bath at 50°C. Transfer to a 2.0 mL reactl-vlal using a toluene
rinse and concentrate to the desired volume using a stream of N2.
9.10 Approximately 1 hour before HRGC/LRMS analysis, add the recovery
standard (^ Cj2-1»2,3,4-TCDD, to give a concentration of 500 ng/mL) to the
residue 1n the react1-v1al. Add an appropriate quantity of toluene. The
final volume should be 100 uL for soil samples, 500 11L for sludge and still
bottom samples and 1 mL for the fly ash samples the correct volume will depend
on the relative concentration of target analytes. Gently swirl the solvent on
the lower portion of the vessel to ensure dissolution of the PCDD's and PCDF's.
Inject an appropriate aliquot (1 or 2 iiL) of the sample Into the GC/MS instru-
ment, using a syringe.
40
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10. GC/MS Analysis
10.1 When toluene 1s employed as the final solvent use of a bonded phase
column from Section 4.3.2 1s recommended. Solvent exchange Into isooctance or
tridecane 1s required for other liquid phases on nonbonded columns.
10.2 Calculate response factors for standards relative to the Internal
standard 1 Ci2-2,3,7,8-TCDD (see Section 11). Add the recovery standard to
the samples prior to Injection. The concentration of the recovery standard in
the sample extract must be the same as that of the calibration standards used
to measure the response factors.
10.3 Analyze samples with selected ion monitoring using 1ons listed in
Table 3. Proof of the presence of PCDD or PCDF exists if the following con-
ditions are met:
10.3.1 The relative retention time of the peak 1n the sample must match that
1n the standard, within the performance specifications of the analytical system
(less than 0.01 units variation 1n relative retention time 1s expected).
10.3.2 The 1sotop1c ratio of 1ons within the parent cluster must agree within
10 percent of the theoretical value as confirmed by the analysis of standards.
10.3.3 For confirmation of a PCDF, molecular ion response (m/z 374, 376,
for example) for diphenyl ethers must be absent at the retention time.
10.4 Quantltate the PCDD and PCDF peaks from the response relative to the
i|Ci2"2»3,7,8-TCDD internal standard. Recovery of the Internal standard
1 Ci2-2,3,7,8-TCDD vs. the recovery standard 13Ci2-l»2,3,4-TCDD must be greater
than 50 percent. Samples with recoveries of less than 50 percent must be
reanalyzed. It 1s recommended that the GC/MS run be divided into 4 scan
monitoring sections monitoring, respectively: (1) 241, 257, 304, 306, 320,
322, 332, 334 (TCDD's, TCDF's + Cio Internal and recovery standards); (2)
275, 291, 338, 340, 342, 354, 356, $58 (PeCDD's and PeCDF's); (3) 311, 327, 372,
374, 376, 388, 390, 392 (HxCDD's and HxCDF's); (4) 345, 361, 406, 408, 410, 422,
424, 426 (HpCDD's and HpCDF's) and (5) 379, 395, 440, 442, 444, 456, 458, 460
(OCDD and OCDF). Cycle time "not to exceed" 1 second/descriptor.
10.5 Additional confirmation using isotoplc ratio measurements must also
be defined for each member of the homologous series.
10.6 In those circumstances where these procedures do not yield a definitive
conclusion, the use of high resolution mass spectrometry or HRGC/MS/MS is
suggested.
11. Calculations
11.1 Determine the concentration of Individual compounds according to the
formulas:
41
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Qfs * As
Concentration, ng/g =
G x AjS x Rf
Where:
Qis s ng of Internal standard 13Ci0-2,3,7,8-TCDD, added to the sample before
extraction.
G » g of sample extracted.
As = area of characteristic ion of the compound of interest.
Ais = ??ea characteristic 1on (m/z 334) of the internal standard,
13C12-2,3,7,8-TCDD.
= response factor of the characteristic ion of the compound of interest
relative to the m/z 334 of 13C12-2,3,7,8-TCDD.
Rf
Response factors are calculated using data obtained from the analysis of stand-
ards according to the formula:
As x Cjs
Rf =
Ais x Cs
Where:
C^s = concentration of the internal standard, *3C12-2,3,7,8-TCDD.
Cs a concentration of the compound of Interest.
Calculate recovery of the internal standard, R^s, 13C12-2,3,7,8-TCDD, in the
sample extract, using for formula:
Ais x Qrs
R1s 3 x 100
Ars x Rfr x Qjj
Where:
Ars = ^?ea of characteristic 1on (m/z 334) of the recovery standard,
13C12-1,2,3,4-TCDD.
Qrs = ng of recovery standard, l3Ci2-l,2,3,4-TCDD added to extract.
The response factor for determination of recovery is calculated using data
obtained from the analysis of standards according to the formula:
*1s x Crs
Rfr =
Ars x *-1s
42
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Where:
Crs s Concentration of the recovery standard, 13Cj2-l»2,3,4-TCDD.
11.2 Report results In nanograms per gram; when duplicate and spiked samples
are reanalyzed, all data obtained should be reported.
11.3 Accuracy and Precision. Table 3 gives the precision data for revised
Method 8280 for selected analytes in the matrices shown. Table 4 gives recovery
data for the same analyses. Table 5 give the linear range and variation of
response factors over the range for selected analyted standards. Table 6 gives
estimated detection limits.
43
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TABLE 1. REPRESENTATIVE GAS CHROMATOGRAPH RETENTION TIMES* OF ANALYTES
50 m 30 m 30 m 30 m
Analyte CP-S11-88 DB-5 SP-2250 DB-225
2,3,7,8-TCDD 23.6 22.8 26.7 37.3
1,2,3,4-TCDD 24.1 22.7 26.5 37.6
1,2,3,4,7-PeCDD 30.0 25.2 28.1 NM
1,2,3,4,7,8-HxCDD 39.5 28.0 30.6 NM
1,2,3,4,6,7,8-HpCDD 57.0 34.2 33.7 NM
2,3,7,8-TCDF 25.2 22.5 26.7 42.5
* Retention time in minutes, using temperature programs shown below.
NM = not measured.
Temperature Programs:
CP-Sil-88 60°C-190°C at 20°/minute; 190#-240# at 5°/minute.
30 m DB-5 170°, 10 minutes; then at 8#/m1nute to 280°C, hold
at 280°C 30 minutes.
SP-2250 70°-320* at 10°/m1nute.
DB-225 70°-230° at 10°/minute.
Column Manufacturers
CP-Sil-88 Chrompack Incorporated, Bridgewater, New Jersey
DB-5, DB-225 J and W Scientific, Incorporated, Rancho Cordova, California
SP-2250 Supelco, Incorporated, Bellefonte, Pennsylvania
44
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TABLE 2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
51 30-60 percent of mass 198
68 Less than 2 percent of mass 69
70 Less than 2 percent of mass 69
127 40-60 percent of mass 198
197 Less than 1 percent of mass 198
198 Base peak, 100 percent relative
abundance
199 5-9 percent of mass 198
275 10-30 percent of mass 198
365 Greater than 1 percent of mass
198
441 Present but less than mass 443
442 Greater than 40 percent of mass
198
443 17-23 percent of mass 442
J. W. Elchelberger, L. E. Harris, and W. L. Budde. Reference compound
to calibrate 1on abundance measurement In gas chromatography-mass
spectrometry. Analytical Chemistry 47, 995 (1975).
45
-------
TABLE 3. PRECISION DATA FOR REVISED METHOD 8280
Analyte Level
(ng/g)
Matrix*
Native
Percent
Compound
Native
+ Spike
N
RSD
2,3,7,8-TCDD
clay
ND2
5.0
4
4.4
soil
378
378
4
2.8
sludge
ND
125
4
4.8
fly ash
ND
46
2
-
still bottom
487
487
4
24
1,2,3,4-TCDD
clay
ND
5.0
3
1.7
soil
ND
25.0
4
1.1
sludge
ND
125
4
9.0
fly ash
38.5
38.5
4
7.9
still bottom
ND
2500
4
-
1,3,6,8-TCDD
clay
ND
2.5
4
7.0
soil
ND
25.0
4
5.1
siudge
ND
125
4
3.1
fly ash
19.1
19.1
2
-
still bottom
227
2727
2
-
1,3,7,9-TCDD
clay
ND
2.5
4
19
soil
ND
25.0
4
2.3
sludge
ND
125.0
4
6.5
fly ash
58.4
58.4
2
-
still bottom
ND
2500
2
-
1,3,7,8-TCDD
clay
ND
5.0
4
7.3
soil
ND
25.0
4
1.3
si udge
ND
125
4
5.8
fly ash
16.0
16.0
4
3.5
still bottom
422
2920
2
-
1,3,7,8-TCDD
clay
ND
5.0
4
7.7
soil
ND
25.0
4
9.0
sludge
ND
125
4
7.7
fly ash
2.6
2.6
3
23
still bottom
ND
2500
2
-
1,2,8,9-TCDD
clay
ND
5.0
4
10
soil
ND
25.0
4
0.6
siudge
ND
125
4
1.9
fly ash
ND
46
2
-
still bottom
ND
2500
2
-
(continued)
46
-------
TABLE 3. (Continued)
Analyte Level (ng/g)
Native
Percenl
Compound
Matrix
Native
+ Spike
N
RSD
1.2,3,4,7-PeCDD
clay
ND
5.0
4
10
soil
ND
25.0
4
2.8
sludge
ND
125
4
4.6
fly ash
25.8
25.8
2
6.9
still bottom
ND
2500
2
-
1,2,3,7,8-PeCDD
clay
ND
5.0
4
25
soil
ND
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
ND
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
-
sludge-'
8760
8780
4
-
fly ash
ND
-
-
-
still bottom
ND
-
-
-
1,2,7,8-TCDF
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
-
(continued)
47
-------
TABLE 3. (Continued)
Compound
Matrix
Analyte Level (ng/g)
Native
Native + Spike
N
Percent
RSD
OCDF
clay
ND
_
soil
ND
-
-
-
sludge
192
317
4
3.3
fly ash
ND
-
-
-
still bottom
ND
-
-
-
1 matrix types:
clay: pottery clay, Westwood Ceramic Supply Co., City of Industry, California.
soil: Times Beach, Missouri, soil 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, resource recovery ash No. 1, as
described in Appendix B.
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 penta-
chlorophenolic wastewaters.
Cleanup of clay, soil and fly ash samples was through alumina column only.
(Carbon column not used.)
2 ND - not detected at concentration injected (final volume 0.1 ml or greater).
3 Estimated concentration out of calibration range of standards.
48
-------
TABLE 4. RECOVERY DATA FOR REVISED METHOD 8280
Native^
Spiked^
Mean
Matrix1
Level
Percent
Compound
(ng/g)
(ng/g)
Recovery
2,3,7,8-TCDD
clay
ND
5.0
61.7
soil
378
-
-
sludge
ND
125
90.0
fly ash
ND
46
90.0
still bottom
487
-
-
1,2,3,4-TCDD
clay
ND
5.0
67.0
soil
ND
25.0
60.3
sludge
ND
125
73.1
fly ash
38.5
46
105.6
still bottom
ND
2500
93.8
1,3,6,8-TCDD
clay
ND
2.5
39.4
soil
ND
25.0
64.0
sludge
ND
125
64.5
fly ash
19.1
46
127.5
still bottom
227
2500
80.2
1,3,7,9-TCDD
clay
ND
2.5
68.5
soil
ND
25.0
61.3
sludge
ND
125
78.4
fly ash
58.4
46
85.0
still bottom
ND
2500
91.7
1,3,7,8-TCDD
clay
ND
5.0
68.0
soil
ND
25.0
79.3
sludge
ND
125
78.9
fly ash
16.0
46
80.2
still bottom
615
2500
90.5
1,2,7,8-TCDD
clay
ND
5.0
68.0
soil
ND
25.0
75.3
sludge
ND
125
80.4
fly ash
2.6
46
90.4
still bottom
ND
2500
88.4
1,2,8,9-TCDD
clay
ND
5.0
59.7
soil
ND
25.0
60.3
sludge
ND
125
72.8
fly ash
ND
46
114.3
still bottom
ND
2500
81.2
(continued)
-------
TABLE 4. (Continued)
Spiked^
Mean
Matrix*
Native?
Level
Percent
Compound
(ng/g)
(ng/g)
Recovery
1,2,3,4,7-PeCDD
clay
ND
5.0
58.4
soil
ND
25.0
62.2
sludge
ND
125
79.2
fly ash
25.8
46
102.4
still bottom
ND
2500
81.8
1,2,3,7,- "eCDD
clay
ND
5.0
61.7
soil
ND
25.0
68.4
sludge
ND
125
81.5
fly ash
ND
46
104.9
still bottom
ND
2500
84.0
1,2,3,4,7,8-HxCDO
clay
ND
5.0
46.8
soil
ND
25.0
65.0
si udge
ND
125
81.9
fly ash
ND
46
125.4
still bottom
ND
2500
89.1
1,2,3,4,6,7,8-HpCDD clay
ND
5.0
ND
soil
ND
25.0
ND
siudge4
8780
125
-
fly ash
ND
-
-
still bottom
ND
-
-
2,3,7,8-TCDD
clay
ND
5.0
64.9
(C-13)
soil
ND
25.0
78.8
sludge
ND
125
78.6
fly ash
ND
46
88.6
still bottom
ND
2500
69.7
1,2,7,8-TCDF
clay
ND
5.0
65.4
soil
ND
25.0
71.1
sludge
ND
125
80.4
fly ash
7.4
46
90.4
still bottom
ND
2500
104.5
1,2,3,7,8-PeCDF
clay
ND
5.0
57.4
soil
ND
25.0
64.4
sludge
ND
125
84.8
fly ash
ND
46
105.8
still bottom
25,600
2500
(continued)
50
-------
TABLE 4. (Continued)
Spiked3
Mean
Native^
Level
Percent
Compound
Matrix1
(ng/g)
(ng/g)
Recovery
1,2,3,4,7,8-HxCDF
clay
ND
5.0
54.2
soil
ND
25.0
68.5
sludge
13.6
125
82.2
fly ash
24.2
46
91.0
still bottom
ND
2500
92.9
OCDF
clay
ND
-
_
soil
ND
-
-
sludge
192
125
86.8
fly ash
ND
-
-
still bottom
ND
"
1 matrix types:
clay: pottery clay, Westwood Ceramic Supply Co., City of Industry, California.
soil: Times Beach, Missouri soil 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, resource recovery ash No. 1, as
described in Appendix B.
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 penta-
chlorophenol wastewaters.
The clay, soil and fly ash samples were subjected to alumina column cleanup,
no carbon column was used.
2 Final volume of concentrate 0.1 ml or greater, ND means below quantification
limit, 2 or more samples analyzed.
3 Amount of analyte added to sample, 2 or more samples analyzed.
4 Estimated concentration out of calibration range of standards.
51
-------
TABLE 5. LINEAR RANGE AND VARIATION OF RESPONSE FACTORS
Analyte
Linear Range Tested (pg)
n**
Mean RF
%RSD
1,2,7,8-TCDF*
50-6000
8
1.634
12.0
2,3,7,8-TCDD*
50-7000
7
0.721
11.9
2,3,7,8-TCDF
300-4000
5
2.208
7.9
* Response factors for these analytes were calculated using 2,3,7,8-TCDF as
the Internal standard. The response factors for 2,3,7,8-TCDF were
calculated vs. 1,3Cj2-l»2,3,4-TCDD.
** Each value of n represents a different concentration level.
52
-------
TABLE 6. DETECTION LIMITS (ppb) FOR RCRA METHOD 8280*.2
Analyte Class Clay Soil Fly Ash Still Bottom3 Sludge
TCDD
1.0
5.0
1.0
500
25
TCDF
0.5
2.5
0.5
250
12
PeCDD
1.5
7.5
1.5
750
38
PeCDF
1.0
5.0
1.0
500
25
HxCDD
2.0
10
2.0
1000
50
HxCDF
1.5
7.5
1.5
750
38
1 The analytes of the class indicated were not quantified below this value.
The instrument detection limit (S = 3 x Noise) for 2,3,7,8-TCDD in standards
is 0.5 ppb when extrapolated for a 10 g sample concentrated to 100 uL.
2 Matrix types:
Clay: Pottery clay, Westwood Ceramic Supply Co., City of Industry, California.
Soil: Times Beach, Missouri, soil blended to form a homogeneous sample. This
sample was analyzed as a performance evaluation sample for the Contract Labora-
tory 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. The 90 percent window was 143 to 469 ng/g.
Fly Ash: Ash from a municipal incinerator, resource recovery ash No. 1, as
described in Appendix B.
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 pentachloro-
phenolic wastewaters.
Cleanup of clay, soil and fly ash samples was through alumina column (carbon
column not used).
3 The still bottom samples were not tested below this level due to high analyte
levels found.
53
-------
APPENDIX B
HOMOGENIZATION AND CHARACTERIZATION OF RESOURCE RECOVERY FLY ASH NO. 1
Experimental: Approximately 5 lb. (2100 g) of resource recovery fly ash No. 1
(RRA No. 1) was homogenized by prolonged tumbling 1n a rotary
extractor. Next, 144 allquots of 10 g each were placed 1n amber
glass bottles fitted with Teflon™ lined screw caps; the allquots
were stored In a freezer. Twelve allquots selected randomly
were extracted by a Soxhlet procedure (SW 846-Method 3540) and
the extracts were submitted for GC/MS analysis (SW 846-Method
8270). The same 12 extracts were also analyzed according to the
IFB GC/MS protocol and the results are Included in Table 1 for
comparison.
Results: Table 1 shows the concentrations of the semi-volatile priority
pollutants (SVPP's) 1n ppm determined in RRA No. 1, together with
the percent recovery of surrogate spikes. Because the concentra-
tions of several SVPP's (e.g., naphthalene, d1-£-butyl phthalate,
chrysene) were lower than those previously determined on 5-g
allquots of RRA No. 1 (see Table 2), a further 12 aliquots (10 g)
were Soxhlet-extracted under rigorously controlled conditions for
optimum extraction efficiency. The results which are shown 1n
Table 3 were generated by taking the mean of all 12 values
determined for each analyte. The results within each set of six
are consistent (generally low percent RSO) and are generally
consistent between the sets.
Conclusions: A total of 24 randomly selected allquots of RRA No. 1 have been
analyzed under two different GC/MS protocols (IFB; SW-846). The
conslsitent results obtained both between the protocols (Table 1)
and between the sample sets Indicate that the material 1s homo-
geneous. Inspection of Lockheed's Statistical Design for Matrix
Characterization for this project Indicates that a power level
of 80 percent 1s attained for all analytes, except benzo(a)-
anthracene, which has a power level of 60 percent. Because of
the reproducible results obtained, RRA No. 1 1s recommended as
suitable for use as a stand-alone reference material.
54
-------
TABLE 1. CONCENTRATION OF SEMI-VOLATILE PRIORITY POLLUTANTS IN
RESOURCE RECOVERY FLY ASH NO. 1 IN PPM
IFB GC/MS Protocol SW-846 GC/MS Protocol4
Pollutant Mean n=12 RSD% Mean n=12 RSD%
Naphthalene 4.8 8.8 4.56 7.5
Acenaphthylene 0.79 17.9 0.58 46.3
Phenanthreneb 23.6 13.6 20.3 5.2
01-n-butyl phthalate 1.50 15.2 1.30 14.6
Dibenzofuran 1.52 7.9 1.46 4.2
Benzo(a)anthracene 0.88 20.8 0.92 21.2
Chyrsene 3.26 13.7 4.11 14.5
Bis(2-ethylhexyl)-
phthalate 1.10 32.1 1.49 44.9
Fluoranthenec 30.5 10.1 31.0 6.2
Pyrenec 9.38 7.6 9.9 8.1
Surrogate Spikes % Recovery
2-Fluorophenol 31.9 16.9 43.7 15.6
Phenol-d5 52.1 21.1 48.2 17.7
Pentafluorophenol 40.3 18.2 41.1 26.8
N1trobenzene-d5 53.8 9.6 65.4 9.1
2-Fluorob1phenyl 83.2 11.0 78.7 6.2
Decafluoroblphenyl 62.9 17.5 71.5 8.0
Pyrene-dlO 69.4 12.5 77.6 9.5
2-Fluoroan1l1ne 2.98 67.1 N.D.
Concentrated extract was diluted 1:1 with dichloromethane for analysis.
^Quantitation 1on m/z 176 (not m/z 178) to avoid saturation.
cQuantitat1on 1on m/z 200 (not m/z 202) to avoid saturation.
55
-------
TABLE 2. SOXHLET EXTRACTION OF RESOURCE RECOVERY FLY ASH NUMBER 1
CONCENTRATION OF SEMI-VOLATILE PRIORITY POLLUTANTS
(ASSUMING 100% EXTRACTION EFFICIENCY) IN PPM
Pollutant Mean RSD% (n=5)
Naphthalene
7.5
4.7
Acenaphthylene
1.18
17.2
Phenanthrene
23.0
12.3
Di-n-butyl phthalate
5.2
33.7
Dlbenzofuran
1.68
21.2
Benzo(a)anthracene
1.82
38.3
Chyrsene
6.28
17.4
Bis(2-ethylhexyl)phthalate
3.24
26.7
Fluoranthene
39.2
16.6
Pyrene
13.5
19.0
Surrogate Spikes % Recovery
2-Fluorophenol
83.7
6.8
Phenol-d5
73.4
12.0
Pentafluorophenol
20.4
78.5
N1trobenzene-d5
64.0
11.3
2-Fluoroblphenyl
105.0
4.0
Decafluoroblphenyl
121.6
17.5
Pyrene-dlO
102.6
8.1
56
-------
TABLE 3. CONCENTRATION OF SEMI-VOLATILE PRIORITY
POLLUTANTS IN RESOURCE RECOVERY FLY ASH NO. 1, PPM
SW-846 GC/MS Protocol
Pollutant Mean, n=lZ RSDT
Naphthalene 4.73 15.1
Acenaphthylene 0.97 17.8
Phenanthrene 18.4 10.9
D1-n-butyl phthalate 1.24 50.2
Dibenzofuran 1.46 18.6
Benzo(a)anthracene 1.28 13.9
Chyrsene 5.18 7.5
B1s(2-ethylhexyl)phthalate 1.05 21.7
Fluoranthene 32.1 25.0
Pyrene 11.3 6.9
Surrogate Spikes % Recovery
2-Fluorophenol 50.9 24.2
Phenol-d5 62.7 11.7
Pentafluorophenol 56.2 13.1
Nitrobenzene-d5 66.1 7.0
2-Fluorob1phenyl 76.4 5.2
Decafluorobiphenyl 58.5 11.8
Pyrene-dlO 90.2 7.4
2-Fluoroan1l1ne 25.6 56.9
57
-------
TECHNICAL REPORT DATA
(Pteast read Instructions on the reverse before completing)
1. REPORT NO. 2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
SINGLE-LABORATORY EVALUATION OF THE RCRA METHOD
FOR ANALYSIS OF DIOXIN IN HAZARDOUS WASTE
5. REPORT DATE
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
F. L. Shore, T. L. Vonnahme, C. M. Hedin,
J. R. Donnelly and W. J. Niederhut*
B. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND AOORESS
Lockheed Engineering and Management Services
Company, Incorporated
P.O. Box 15027
Las Veaas. Nevada 89114
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
Contract Number 68-03-3050
12. SPONSORING AGENCY NAME AND ADORESS
Environmental Monitoring Systems Laboratory - LV, NV
Office of Research and Development
U.S. Environmental Protection Agency
Las Veaas. NV 89114
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/07
is. supplementary notes *Current address - Environmental Research Center, Quality
Assurance Laboratory, University of Nevada, Las Vegas, NV 89154
Project Officer - Stephen Billets, Environmental Monitoring
is.abstract 5ystems Laboratory, Las Vegas, Nevada 89114
Single-laboratory testing of RCRA Method 8280 for the analysis of chlorinated dibenzo-
p-diox1ns and dlbenzofurans has been initiated on sample matrices Including pottery
clay soil, a Missouri soil, a fly ash, a still bottom from a chlorophenol-based
herbicide production process, and an Industrial process sludge. This analytical
method was Intended for use In the determination of chlorinated dioxin and dibenzo-
furan homologs with four, five, or six chlorine atoms per molecule. Revisions to the
method that were found necessary for satisfactory analytical performance have been
developed and have been incorporated into a revised version of the method. Single-
laboratory testing of method 8280 with minor revisions demonstrated satisfactory
performance for the target analytes on soil and fly ash samples. Further modifica-
tion and elaboration of sample cleanup procedures were necessary for analysis of the
still bottom and industrial sludge samples.
17. Jl KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThiMReport/
UNCLASSIFIED
21. NO. OF PAGES
20. SECURITY CLASS (This page f
UNCLASSIFIED
22. PRICE
EPA form 2220-1 (R««. 4-77) previous coition is obsolete
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