£EPA
United States
Environmental Protection
Agency
Industrial Environmer
itory
Research Triangle Park NC 2771 1
Level 1 Environmental
Assessment Performance
Evaluation
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development. U.S. Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports m this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of. and development of. control technologies for energy
systems; and integrated assessments of a wide'range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.
-------
EPA-600/7-79-032
February 1979
Level 1 Environmental
Assessment Performance
Evaluation
by
Eva D. Estes, Franklin Smith, and Denny E. Wagoner
Research Triangle Institute
P.O. Box12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2612
Task No. 21
Program Element No. INE624
EPA Project Officer: William B. Kuykendal
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U. S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U. S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
-------
ABSTRACT
This report presents the results of a two-phased evaluation, of Level 1
environmental assessment procedures. Phase I was a field evaluation of the
Source Assessment Sampling System (SASS). Three sample tests were made with
two SASS trains sampling simultaneously and from approximately the same
sampling point in a horizontal duct. A Method 5 train was used to estimate
the "true" particulate loading. The sampling systems were located upstream
of the control devices to insure collection of sufficient material for
comparison of total particulate, particle size distribution, organic classes,
and trace elements. Phase II consisted of providing each of three partici-
pating organizations with three types of control samples to challenge the
spectrum of Level 1 analytical procedures: an artificial sample in methy-
lene chloride, an artificial sample on a flyash matrix, and a real sample
composed of the combined XAD-2 resin extracts from all Phase I SASS runs.
Estimates of intralaboratory and interlaboratory precision are made.
111
-------
CONTENTS
Abstract iii
Figures vi
Tables vii
Abbreviations ix
Acknowledgments x
1. Introduction 1
2. Summary and Conclusions 3
Phase I: Field evaluation of the SASS 3
Phase II: Verification of the Level 1 analytical
procedures 4
3. Discussion of the Experimental Test Plan 5
Phase I: Field evaluation of the SASS 5
Phase II: Verification of the analytical scheme. ... 10
4. Results of SASS Evaluation 13
Particulate concentrations determination 13
Particle size fractionation 16
Organic extractables 16
Organics in LC fractions 16
Functional groups identified by IR 20
Categories, subcategories, and specific compounds
identified by LRMS 20
Organic categories summary 20
Arsenic, mercury, and antimony comparisons 24
5. Results of Analytical Methods Evaluation 26
Organic analysis results 26
Inorganic analysis results 44
References 53
Appendix A: Composition of Phase II Artificial Samples 54
Appendix B: Phase I Infrared Spectroscopy Results: Functional
Groups Identified in Liquid Chromatography Fractions. . 61
Appendix C: Categories Identified in Phase I Organic Extracts
by LRMS 75
Appendix D: Subcategories, Specific Compounds Identified in Phase I
Organic Extracts by LRMS 80
Appendix E: Graphical Representation of Phase II IR Results 92
Appendix F: Phase II IR Results: LC Fractions 99
Appendix G: LRMS Results: Categories Identified in Phase II
Samples 133
iv
-------
CONTENTS (continued)
Appendix H: Additional Analytical Results From Lab C 143
Appendix I: LRMS Results: Specific Compounds Identified in
Phase II Samples 148
-------
FIGURES
Number Page
1 Test Site Configuration for Field Evaluation
of the SASS 7
2 Comparison of Particle Size Fractionation of two
SASS's 17
vi
-------
TABLES
Number
1 Procedures for Analysis of a Selected Pair of SASS
runs 8
2 Procedures for Analysis of Phase II Samples 11
3 Particulate Concentrations mg/m3 15
4 Analysis of Variance Table 15
5 Organic Extractables (mg/m3) 18
6 Organic Extracts Summary (SASS 1/SASS 2) 19
7 Functional Groups in SASS Samples Identified by
IR (Before LC Separation) 21
8 Organic Categories in SASS Samples 23
9 Arsenic, Mercury, and Antimony Determinations 25
10 TCO/GRAV Results: Artificial Sample in CH2Cl2(mg) 27
11 TCO/GRAV Results: Artificial Sample on Flyash
Matrix (mg) 28
12 TCO/GRAV Results: Field Sample, XAD-2 Extract (mg) .... 29
13 TCO/GRAV Results: Artificial Sample in CH2C12,
Aliquot l(mg) 31
14 TCO/GRAV Results: Artificial Sample in CH2C12,
Aliquot 2(mg) 32
15 TCO/GRAV Results: Artificial Sample in CH2C12,
Aliquot 3(mg) 33
16 TCO/GRAV Results: Artificial Sample on Flyash Matrix,
Aliquot l(mg) 34
17 TCO/GRAV Results: Field Sample, XAD-2 Extract,
Run l(mg) 35
18 IR Results: Artificial Sample in CH2C12, '
Aliquot 1 37
19 IR Results: Artificial Sample on Flyash Matrix,
Aliquot 1 38
20 IR Results: Field Sample, XAD-2 Extract, Run 1 39
21 LC Fractions Which Triggered LRMS vs. LRMS Obtained .... 41
22 Categories Identified in Artificial Sample in CH2C12,
Aliquot 1 42
23 Specific Compounds Identified by LRMS in Artificial
Sample in CH2C12, Aliquot 1 43
24 Categories Identified by LRMS in Artificial Sample on
Flyash Matrix, Aliquot 1 45
25 Specific Compounds Identified by LRMS in Artificial
Sample on Flyash Matrix, Aliquot 1 46
28 SSMS Results: Artificial Sample on Flyash Matrix
(pg/g) 47
vii
-------
TABLES (continued)
Number Page
29 Comparison of As and Sb by SSMS and by SDDC and
AA, Respectively 49
30 Results of Tests of Significance and Sample
Statistics by Element 51
viii
-------
ABBREVIATIONS
AA Atomic Absorption
ADL Arthur D. Little, Inc.
ANOVA Analysis of Variance
CV Coefficient of Variation
GC Gas Chromatography
Grav Gravimetric
HC Hydrocarbon
IR Infrared
LC Liquid Chromatography
LRMS Low Resolution Mass Spectroscopy
RTI Research Triangle Institute
SASS Source Assessment Sampling System
SDDC Silver Diethyldithiocarbamate
SoRI Southern Research Institute
SSMS Spark Source Mass Spectrometry
TCO Total Chromatographable Organics
ix
-------
ACKNOWLEDGMENTS
The work described in this report was performed under contract 68-02-
2612, Task 21, with the U. S. Environmental Protection Agency. Special
acknowledgment is given to EPA Project Officer, Mr. William B. Kuykendal,
and EPA Task Leader, Dr. Ben Smith, for many helpful discussions.
The efforts of the following organizations are gratefully acknowledged:
Southern Research Institute, TRW Defense and Space Systems Group, and Radian
Corporation for their participation in the field sampling phase of the
project and for their analysis of the control samples; and Arthur D. Little,
Inc., for analyzing the field samples and preparing, analyzing, and distribut-
ing the control samples.
-------
SECTION 1.0
INTRODUCTION
An experimental program designed to evaluate the source assessment
sampling system (SASS) and the associated Level 1 analytical procedures has
been completed. The project was conducted in two phases. Phase I consisted
of a field evaluation of the SASS involving simultaneous sampling with two
SASS trains and a Method 5 train. Results of Phase I are used to estimate
within- and between-train precisions for particulate, organic, and inorganic
sampling, and to estimate the biases of the SASS trains with respect to
Method 5 for total particulate determinations. Phase II consisted of an
interlaboratory evaluation of the analytical methods involving the analysis
of split samples by participating laboratories.
The Research Triangle Institute (RTI) coordinated the experimental
program with Arthur D. Little, Inc. (ADL), Southern Research Institute
(SoRI), TRW, and Radian Corporation. ADL prepared all XAD-2 resin used in
the field sampling; analyzed all the field samples collected in Phase I of
the program; and prepared, analyzed, and distributed the control samples
used in Phase II. SoRI and TRW each provided a field crew and a SASS train
for Phase I and participated in Phase II by analyzing the control samples
provided by ADL. Radian Corporation provided a field crew and a Method 5
train for Phase I and participated in Phase II by analyzing the control
samples.
The objectives of this project were to evaluate both the SASS and the
analytical procedures. Assessment of field crew and/or analyst performance
was not a program objective. However, this study bears out the prediction
that, with training, a good crew can learn to operate the SASS successfully.
No major difficulties were encountered during the sampling phase. Actions
taken to eliminate or minimize extraneous sources of variability in the
field evaluation of the SASS included the following:
-------
1. Each participating organization was requested to provide a crew
experienced in the operation and field use of the SASS.
2. Field crews were briefed on and directed to use the approved and
documented Level 1 sampling procedures (1).
3. RTI provided onsite coordination of the field sampling activities.
A. Calibration checks were made on the volume measurement systems
(dry gas meters) of the SASS trains and on the gas velocity measure-
ment systems of the two SASS trains and the Method 5 train.
5. All field samples were analyzed by one organization (i.e., ADL),
eliminating the between-laboratory component of variability of the
analytical methods.
In an effort to minimize analyst/laboratory biases in Phase II of the
program, RTI personnel visited each organization to discuss the analytical
procedures and to review the laboratory facilities and apparatus to be used
in the analysis of the control samples. Also, as RTI analyzed the data for
the final report, outliers or suspicious data were brought to the attention
of the reporting organization for verification and/or correction as appro-
priate. For this test, laboratories were allowed to repeat calculations but
were not allowed to repeat analysis.
A brief summary and interpretation of the results of both phases of the
program are contained in Section 2.0 of this report. A description of the
test plan for the field evaluation of the SASS and for the interlaboratory
evaluation of the analytical procedures is given in Section 3.0. Results of
the field evaluation of the SASS are presented and discussed in Section 4.0.
The interlaboratory evaluation of the analytical procedures is described in
Section 5.0.
-------
SECTION 2.0
SUMMARY AND CONCLUSIONS
PHASE I: FIELD EVALUATION OF THE SASS
The SASS was evaluated under field conditions on a preselected, stable
source characterized by high organics and high particulate loadings. Samples
were collected with two SASS trains and a Method 5 train running simultane-
ously. Three complete sample tests were made, each test consisting of two
SASS runs and a Method 5 run. The relative positions of the trains were
fixed with the probes of the two SASS trains positioned at a point of aver-
age duct velocity and within a few inches of each other. The Method 5 train
was positioned downstream from the SASS train and operated according to the
Federal Register method; i.e., the duct was traversed, and isokinetic samp-
ling conditions were maintained (3). To insure consistency, all analytical
work for Phase I was done by one organization.
Particulate Loading and Sizing
For each SASS train run, the particulate on the filter and in each
cyclone was dried and weighed to compare particle sizing between trains.
The total particulate catches were then used to determine particulate load-
ing for comparison to Method 5.
Results show the following:
1. Particle sizing compared very well between SASS's for the
three tests.
2. Particulate concentrations determined by the SASS's compared
very well with Method 5, the largest difference being within
20 percent.
3. The estimated precision between trains given as a standard
4
deviation is 36 mg/m (10 percent on a relative basis).
-------
Collected Qrganics
A complete Level 1 organics analysis was carried out on the pair of SASS
runs from Test 2. For this set, the organic material collected by the SASS's
agreed well in quantity and composition (i.e., volatile, nonvolatile, and
categories) and was collected proportionally in corresponding SASS components.
Collected Inorganics
For the same pair of SASS runs, mercury, arsenic, and antimony were deter-
mined on the combined second and third impingers by atomic absorption. For
these limited analyses, the data for each element agree within a factor of two.
PHASE II: VERIFICATION OF THE LEVEL 1 ANALYTICAL PROCEDURES
Three aliquots of each of three sample types were supplied to each of
the three participating organizations for analysis by current Level 1 proce-
dures. The three sample types were:
1. A known, artificial, liquid sample containing 16 components.
2. A real particulate sample obtained from a source significantly
different from the one selected for Phase I sampling.
3. The combined XAD-2 extracts from the SASS runs in Phase I.
A full Level 1 analysis was performed on one aliquot of each of the
three sample types; the remaining aliquots were analyzed using a reduced
Level 1 scheme.
Certain methods employed in the organic analysis scheme are still being
refined, and interpretation of the organic data from complex sources can be
an involved process requiring great attention to detail. However, from this
preliminary analysis of Phase II data, it appears that the organic analysis
scheme can yield results of adequate quality to satisfy Level 1 requirements
provided that judicious care is exercised by the analyst to follow specified
procedures and to utilize all the analytical data generated by the scheme in
interpreting individual blocks of data.
Results of the inorganic sample preparation and SSMS analysis scheme
indicate that, for some elements, variability in the analytical phase alone
may be exceeding the allowable factor of 2 to 3 in the Level 1 procedures.
It is expected that standardization of procedures among contractors will
reduce this variability.
-------
SECTION 3.0
DISCUSSION OF THE EXPERIMENTAL TEST PLAN
Procedures for Level 1 environmental assessments for both sample
collection and sample analyses have been specified by the Process Measure-
ments Branch (PMB) of the Industrial Environmental Research Laboratory
(IERL) (1). In order for the Level 1 procedures to be effective, the preci-
sion and accuracy of both the sample collection and sample analysis phases
of the measurement process must be sufficient to satisfy Level 1 data
quality requirements.
The primary procedure for characterizing gaseous process streams in
environmental assessments is to use the SASS for sample collection and
specified analytical methods for subsequent sample analysis. The SASS and
some of the analytical methods, at least for this application, are still in
the developmental stage to the extent that prior to this study they had not
been subjected to collaborative (or interlaboratory) tests. The purposes of
this project were to evaluate the SASS under field conditions (Phase I) and
to conduct an interlaboratory evaluation of the associated analytical methods
(Phase II).
PHASE I: FIELD EVALUATION OF THE SASS
The SASS train evaluation test planstarting with source selection
criteria, continuing through sampling requirements, and ending with direc-
tions for sample analysesis defined in the following paragraphs.
Source Selection Criteria
Criteria used in the source selection process were as follows:
1. The process stream should be sufficiently high in organics and
particulate to provide a stiff challenge of the SASS train.
2. The process stream should be sufficiently stable to allow for
comparison of data between days or tests.
-------
3. The process stream must be amenable to this test in terms of space
for simultaneous operation of two SASS trains and a Method 5
train, available electrical power to operate the trains and two
mobile laboratories, and a physical stack or duct configuration
such that sampling port locations for Method 5 are consistent with
criteria set forth in EPA Reference Method 1 (2).
Examination of data from previous tests revealed a site which met the
above conditions. The plant process was continual, the grain loading was
3 3
194.5 mg/m (0.085 gr/ft ) when sampling prior to the control device, and
analysis of samples collected yielded significant concentrations of organic
compounds.
Field Sampling
Samples were collected with the two SASS trains and the Method 5 train
running simultaneously. Three complete sample tests were made. The rela-
tive positions of the trains were fixed with the probes of the two SASS
trains positioned at a point of average duct velocity and within a few
inches of each other. The Method 5 train was positioned downstream from the
SASS train and operated according to the Federal Register method; i.e., the
duct was traversed and isokinetic sampling conditions were maintained (3).
The test site configuration is shown in Figure 1.
A calibration check of the dry gas meters showed the SASS's to agree
within 3 percent on volume measurements. A comparison of the S-type pitot
tubes on the SASS's against a standard pitot tube yielded coefficients of
0.84 and 0.89 as compared to the 0.85 ± 0.02 value assumed for well-manufac-
tured S-type pitot tubes.
Analysis Scheme for Field Samples
To insure consistency, all analytical work for Phase 1 was done by one
organization. Table 1 summarizes the analyses performed on the pair of SASS
runs from one test. For the other two tests, the only analyses performed
were gravimetric analyses of particulate for the cyclones, filter, and
rinse. The analysis scheme of Phase I is described in the following listing.
-------
35' -* 14'
TOP VIEW
66'
*
1
1
^J
\
1
1
1
1
V L
13' 1"
METHOD SASS.
SIDE VIEW
\
(
\
4
T
f 8'r
i^- 1
Pi«r Jy
200° F
SASS1
METHOD 5
TRAVERSE POINTS
13*1"
T
6-r
1
Figure 1. Test site configuration for field
evaluation of the SASS.
-------
TABLE 1. PROCEDURES FOR ANALYSIS OF A SELECTED
PAIR OF SASS RUNS
SAMPLE
10 /zm CYCLONE
3 Mm CYCLONE
1 Mm CYCLONE
FILTER
XAD-2 CARTRIDGE
ORGANIC RINSE*
(SORBENT MODULE)
2ND AND 3RD
IMPINGERS
o
o
X
o
UJ
%
cc
0
^
^
*r
*
_
o
SOXHLET
EXTRACTII
^_
7*
--
I
o
UJ
UJ
oc
%
>
cc
0
>
<
cc
o
+
o
p
-*-
^
V
a
--
A
w-
>
<
oc
0
+
o
g
--
A
w^
(O
oc
J
1
cc
-«
_A
V
2
CO O
PARR BOM
COMBUSTII
CO
i
As/Sb/Hg
_A
^W
Sample volume was measured and TCO determined prior to drying.
8
-------
1. Particulate
A. For each SASS train run, the particulate on the filter and in
each cyclone was dried, then weighed, and the total weight of
particulate determined. The particulate for each Method 5
run was also dried and weighed. Weighings were done in the
field by one person. This allowed for a comparison of the
SASS trains to each other and to the Method 5 for each test
(same day) and on a day-to-day basis.
B. For one test (two SASS trains and a Method 5 run simultane-
ously) , the organics were extracted (soxhlet extraction) from
the particulates and the particulates reweighed. The SASS
particulate extracts were then analyzed for volatile (TCO)
and nonvolatile (Grav) organic material and subjected to a
full Level 1 organics analysis, including LC-IR-LRMS.
2. XAD-2 Module
A. For each SASS run, the total weight (TCO + Grav) was to be
determined for the condensate and for the combined XAD-2
extract and module rinse. However, the source yielded no
condensate, and the extracts were inadvertently combined for
Phase II before obtaining TCO and Grav data on the individual
runs. In addition, the module rinses were not combined with
the extracts from the XAD-2 module as specified in the orig-
inal test plan since the methano1 in the rinse solution would
have interfered with class separation during LC fractionation.
Instead, the rinses were evaporated separately to a tarry
solid and introduced onto the silica surface.
B. On the same pair of runs selected for the particulate organic
analysis, the above TCO + Grav determinations were followed
by eight class separations with a TCO + Grav determination on
each of the fractions. The fractions were also analyzed by
the IR-LRMS scheme.
3. Impingers
For the same pair of runs selected for particulate organics anal-
ysis and XAD-2 eight class separation, Hg, As, and Sb were deter-
-------
mined on the combined second and third impingers by current Level
1 methods. No analyses were done on the impinger solutions for
the remaining tests.
PHASE II: VERIFICATION OF THE ANALYTICAL SCHEME
Three aliquots of each of three sample types were supplied to each of
the three participating organizations for analysis by current Level 1 proce-
dures. The three sample types were as follows:
1. A known, artificial, liquid sample containing 16 components; the
three aliquots were not identical but contained different amounts
of certain components;
2. A real particulate sample obtained from a source significantly
different from the one selected for Phase I sampling; the three
aliquots were identical;
3. The combined XAD-2 extracts from all the SASS runs in Phase I; the
three aliquots were identical.
The samples were coded and specific instructions for the analytical
work to be done on each were provided. Each participant did a full Level 1
analysis on one aliquot of each of the above three sample types. For the
other two aliquots of each type, there was a reduced analysis scheme.
Analysis Scheme for Control Samples
Procedures for analysis of the control samples for Phase II of the
evaluation are summarized in Table 2 and discussed in the following para-
graphs .
1. Sample 1
A. Aliquot 1. This aliquot was taken through a complete Level 1
organic analysis beginning with a TCO + Grav. The sample was
then separated into eight fractions by LC with a TCO + Grav
and IR-LRMS on each fraction.
B. Aliquot 2 and 3. The analysis of these aliquots involved a
TCO + Grav, eight class separation by LC, and TCO + Grav on
each of the eight fractions.
10
-------
TABLE 2. PROCEDURES FOR ANALYSIS OF PHASE II SAMPLES
SAMPLE 1
ALIQUOT 1
ALIQUOTS 2 AND 3
SAMPLE 2
ALIQUOT 1
ALIQUOT 2 AND 3
SAMPLE 3
ALIQUOT 1
ALIQUOT 2 AND 3
SOXHLET
EXTRACTION
A
I*
_
1
o
+
o
o
H
,
,-
'
,
S
1
O
+
o
o
H
.
...
W5
*J
fH
h-(
PARR BOMB
COMBUSTION
w
3 ^
hJ CO
0-, ^-
00
W X
en CQ
CO <
11
-------
2. Sample 2
A. Aliquot 1. The analysis of this sample type followed the
Level 1 scheme for particulates. One portion of the sample
was extracted and a TCO + Grav performed on the extract. The
extract was then separated into eight fractions by 1C and a
TCO + Grav and IR-LRMS performed on each fraction. The
remaining particulate was Parr-bomb combusted and analyzed by
SSMS and by approved Level 1 procedures for As/Hg/Sb.
B. Aliquot 2 and 3. These two aliquots were extracted and a TCO
+ Grav performed on the extract.
3. Sample 3
A. Aliquot 1. Analysis of this combined extract sample started
with a TCO + Grav followed by the eight class LC separation
with a TCO + Grav and IR-LRMS on each of the eight fractions.
B. Aliquots 2 and 3. These two aliquots involved only a TCO +
Grav analysis.
Composition of Artificial Control Samples
The compositions of the artificial samples in methylene chloride and
the artificial sample on a flyash matrix are given in Appendix A. During
the analysis phase these compositions were known only to ADL, RTI, and EPA.
12
-------
SECTION 4.0
RESULTS OF SASS EVALUATION
The purpose of an interlaboratory test is, within the project con-
straints, to do the following:
1. Where possible, compare the experimental system results with
reference methods or standard material (accuracy).
2. Compare results between similar sets of equipment operated by
different laboratories (reproducibility and interlaboratory preci-
sion) .
3. Compare duplicate results from the same system operated by the
same laboratory (repeatability or intralaboratory precision).
Measurements for which data are available and the order in which they
will be discussed are as follows:
1. Particulate concentration determinations allowing comparison of
the SASS's with Method 5 and with each other for three tests.
2. Particle size fractionation between SASS's for three tests.
3. Total (volatile and nonvolatile) organics by LC fractions between
SASS's for one test.
4. Organic categories in samples between SASS's for one test.
5. IR results (functional groups) for samples between SASS's.
6. Categories, subcategories, and specific compounds identified by
LRMS between SASS's.
7. Organic material collected between SASS's for one test.
8. Arsenic, mercury, and antimony determinations for one sample
between SASS's.
PARTICULATE CONCENTRATIONS DETERMINATION
Three complete tests were made with the two SASS's and the Method 5
train sampling simultaneously as described in the test plan discussion.
This experiment was designed so that the results could be analyzed by
analysis-of-variance (ANOVA) methods. Particulate concentration determin-
13
-------
ations are given by train and by test number in Table 3. The corresponding
ANOVA table is shown as Table 4.
Basically, the ANOVA is an analysis of differences in means based on
the fact that if the means of subgroups differ significantly, the variance
of the combined groups is much larger than the variances of the separate
groups (ref. 4). For this experiment, a two-way classification ANOVA is
used wherein the variation among trains and the variation among tests are
estimated and individually compared to the estimated experimental error
(residuals in Table 4). The objectives of this analysis are to test the
following hypotheses: *
1. Hypothesis 1: There are no differences between trains.
2. Hypothesis 2: There are no differences between tests.
If the first (second) hypothesis is true, then from Table 4
22 22
-------
TABLE 3. PARTICULATE CONCENTRATION mg/m3
Test #
Test 1
Test 2
Test 3
Total
SASS 1
408
399
353
1,160
SASS 2
337
349
315
1,001
M 5
342
322
371
1,035
Train
Total
1,087
1,070
1,039
3,196
a = 28 mg/m3 (8%) WITHIN TRAIN PRECISION.
(a2 + a)^ = 36 mg/m3 (10%) BETWEEN TRAIN PRECISION.
TABLE 4. ANALYSIS OF VARIANCE TABLE
Source
Tests
Trains
Residual
Total
Sum of squares
395
4,674
3,154
8,223
Degrees
of
freedom
2
2
4
8
Mean square Estimate of
197 a2 + 3a 2
r
2,337 a2 + 3at2
789 a2
15
-------
2
For between tests, the component of variance given by CTr as calculated
from Table 4 resulted in a negative value. That variance component is then
assumed to be zero or very small compared to experimental error; i.e.,
a «a.
The results of this evaluation indicate that SASS's precision and
accuracy were not significantly different from the precision and accuracy of
the Method 5 determinations.
PARTICLE SIZE FRACTIONATION
Particle matter is divided into four size fractions by the SASS using
three cyclones and a filter in series. From Table 3, comparison of particu-
late concentration measurements can be made. The particulate concentration,
as determined from each cyclone and the filter, is given as a percent of the
total concentration determined by the train in Figure 2. As seen from the
figure, results from corresponding components of the SASS's compare very
well for all tests.
ORGANIC EXTRACTABLES
Extracting organic matter from SASS samples is an important procedure
in the analysis process. Table 5 compares the volatile (TCO) and nonvolatile
(Grav) organic contents of the samples taken from corresponding components
of the SASS's. The data show that organic material collected by the corre-
sponding components was comparable in quantity (total) and in composition
(volatile and nonvolatile).
ORGANICS IN LC FRACTIONS
In the Level 1 analysis procedures, the sample extract is separated by
silica gel liquid chromatography and a solvent gradient series into 8 frac-
tions of varying polarity. TCO and gravimetric analyses of each fraction
are done to determine the distribution of the sample by the various class
types.
Comparison of the distribution of the samples in terms of volatile and
nonvolatile organics by LC fractions is given in Table 6.
As seen from the table, the totals (I) across all fractions for TCO and
Grav agree very well. The comparison for individual fractions with few
exceptions is good.
16
-------
40
x 35
u
< 30
u
3 25
° 20
o
i- 15
z
| 10
UJ
°- 5
0
_
>^
77^
///
y//
/ //
w-
f////
////
///
///.
///
i
',-//
///
///
///
///
i
p^-4
Cydone Cydone Cydone
"| SASS2
1 SASS1
'x>
///
///
'//
i
11 -'1,
Filter
COMPARISON OF PARTICLE SIZE FRACTIONATION (Test 1)
40 j-
x 35
< 30
o
< 25
E 20
O 4 C
H-
E 10
OC
UJ e
Q. 5
0
\
U n n
«A 1 1
IUM JM "W
Cydone Cydone Cydone
"
Filter
COMPARISON OF PARTICLE SIZE FRACTIONATION (Test 2)
40
x 35
u
£ 30
u
< 25
° 20
u.
° 15
B 10
oe
UJ -
a. 5
0
-
-
-
V77/
-------
TABLE 5. ORGANIC EXTRACTABLES* (mg/ra3)
XAD-2 MODULE
CYCLONE (EXTRACT) XAD-2 (EXTRACT) (RINSE)
TCO
GRAV
TOTAL
SASS 1
0.03
1.65
1.7
SASS 2
0.01
1.58
1.6
SASS 1
3.41
10.2
13.6
SASS 2
3.58
8.99
12.6
SASS 1
69
69
SASS 2
81
81
*Totals after LC fractionation.
18
-------
TABLE 6. ORGANIC EXTRACTS SUMMARY
(SASS 1/SASS 2)
Cyclone Extract
Total Organics
mg/m3
TCO, mg
Grav, mg
LC 1
0.03
0.01
0.8
0.2
0
0
LC 2
<0.01
0
<0.1
<0.1
0
0
LC 3
0.54
0.61
<0.1
<0.1
16.8
19.2
LC 4
0.22
0.15
<0.1
<0.1
6.8
4.8
LC 5
0.10
0.06
<0.1
<0.1
3.2
2.0
LC 6
0.68
0.73
<0.1
<0.1
21.2
23.2
LC 7
<0.01
0.01
<0.1
<0.1
0
0.4
LC 8
0.10
0
<0.1
<0.1
3.2
0
I
1.7
1.6
1.0
0.5
51
50
XAD-2 Extract
Total Organics
mg/m3
TCO, mg
Grav, mg
LC 1
0.54
0.33
5.2
2.6
13
7.5
LC 2
0.71
2.4
19
35
3.3
38
LC 3
8.1
8.8
73
58
182
216
LC 4
0.95
0.59
6.7
1.7
23
17
'LC 5
0.35
0.25
3.7
1.1
7.3
6.7
LC 6
1.5
0.93
5.3
5.7
41
23
LC 7
0.47
0.24
0.1
0.1
15
7.3
LC 8
0.01
0.07
0.2
2.1
0
0
I
12.6
13.6
113
106
284
315
Sorbent Module Rinse
Total Organics
mg/m3
Grav, mg
LC 1
1.6
1.6
49.9
51.7
LC 2
1.3
1.3
39.5
41.4
LC 3
8.9
14.4
277
455
LC 4
19.7
28.5
612
900
LC 5
12.9
6.6
400
207
LC 6
9.9
8.5
306
269
LC 7
14.6
16.9
454
533
LC 8
0
3.1
0 2
98.2 2
I
69
81
,138
,555
-------
FUNCTIONAL GROUPS IDENTIFIED BY IR
IR spectroscopy is used in the Level 1 environmental assessment proce-
dures to determine the types of functional groups present in a sample.
Table 7 compares the results of the IR analyses of the samples before LC
separation. The band position (v, cm" ), intensity [weak (W), medium (M),
or strong (S)J, and functional group assignments are indicated. Agreement
is good between samples taken from corresponding components of the two SASS
trains. Bands identified in only one of the two samples are of weak intensity.
The IR results for the LC fractions of the samples are given in Appendix B.
CATEGORIES, SUBCATEGORIES, AND SPECIFIC COMPOUNDS IDENTIFIED BY LRMS
A low resolution mass spectrum (LRMS) is obtained on all LC fractions
3
that exceed the concentration threshold (TCO + Grav > 0.5 mg/m ) in order to
determine the principle compound types present in each fraction.
Interpretation of the LRMS spectra is guided by knowledge of the LC
separation scheme and information from the IR spectra. When results are
reported, increasingly more specific data are presented as the complexity or
simplicity of the spectra will allow. The first level of reporting is
identification of compound classes. Appendix C compares the categories
identified in the organic extracts of samples taken from corresponding
components of SASS 1 and SASS 2. Molecular weight range and composition are
estimated with ratings of 100 - major, 10 = minor, and 1 = trace. The more
specific data (subcategories and compounds) are reported in Appendix D.
ORGANIC CATEGORIES SUMMARY
Identification and quantification of organic categories in process
streams are the ultimate goals of a Level 1 organics analysis. Table 8
lists the categories and their concentrations for one set of SASS runs as
determined by the combination of all organic analytical methods (i.e., TCO +
Grav, IR, and LRMS). As seen in the table, the categories compare well
across trains, both qualitatively and quantitatively.
3 3
Qualitatively, only inorganics at 0.1 mg/m and silicones at 0.1 mg/m
were identified in the SASS 1 sample and not the SASS 2 sample. Quantita-
tively, when the concentration levels are considered, only the difference in
the heterocyclic 0 concentrations appears to be much larger than desired.
20
-------
TABLE 7. FUNCTIONAL GROUPS IN SASS SAMPLES IDENTIFIED BY IR
(BEFORE LC SEPARATION)
a. Cyclone Extracts
v> cm"1
3,050
2,950, 2,920, 2,850
1,720
1,600
1,450
1,380
1,280
810
750
SASS 1
Intensity
M
M
S
M
M
W
M
M
S
Assignment
aromatic CH
aliphatic CH
imide, carbamate,
lactone, dialkyl
ketone, a-Ci
ketone
ring vibrations
CHg , CHs
113, SiCH=CH2
SiCH3, C-0-N02
SiCH3, substituted
pyridine
aromatic, fused
rings
b. XAD-2 Extracts
3,400
3,050
2,950-2,930
1,700
1,600
VW (broad)
M
M
W
\
M
NH, OH
aromatic CH
aliphatic CH
ester, amide,
ketone, unsubsti-
tuted ami dine
HC£, carbamate,
imide,
C-N=0, N-C=N,
ring vibrations
v, cm l
3,050
2,920
1,920
1,710
1,660
1,600
1,450
1,250
810
750
SASS
Intensity
M
M
W
M
M
M
M
M (broad)
M
S
2
Assignment
unsaturated CH
saturated CH
allene, C=C=CH2
imide, carbamate,
dialkyl ketone, ester
ketone, C=N, C=C
aromatic ring
CH2, aromatic CH, CH3
ester, ether
substituted pyridine,
substituted aromatic,
C=CH, fused ring
compound
aromatic, fused rings,
substituted pyridine
3,400
3,050
2,950-2,930
1,700
1,600
W (broad)
M
M
W
M
OH, NH
a roma tic CH
aliphatic CH
ester, amide, ketone,
unsubstituted ami dine
HC£, carbamate, imide
C-N=0, N-C=N,
ring vibrations
ro
(cont inued)
-------
TABLE 7 (continued)
b. XAD-2 Extracts (con.)
\), cm
1,500
1,460-1,420
1,180
850-700
c . Sorbent
3,050
2,920
1,615, 1,600
1,460, 1,450
1,430
1,380
1,300
1,260
1,240
840-700
740
SASS 1
1 Intensity
W
M
M
S(multiple)
Module Rinses
M
W
M
, 1,440 M
W
W
W
W
S (multiple)
S
Assignment
ring vibrations
Si-aromatic, SCH2~,
3-substituted
pyridine, alipha-
tic and aromatic
CH, SiCH2-
ester, SiO-CH3,
C3P=0
substituted aroma-
tic or fused rings
unsaturated CH
saturated CH
ring vibrations,
C=C, N-C=N
CH2 , CH3 , CH3
aromatic, CH2C£,
SCH3 , SCH2
CH3
S-CH3
CH2C£
S-CH2
aromatic, fused
rings
C-C£
SASS 2
v, cm"1
1,500
1,460-1420
1,180
850-700
Intensity
W
M
M
S(multiple)
Assignment
ring vibrations
phenyl-Si, S-CH2-,
3-substituted pyridine,
aliphatic and aromatic
CH, Si-CH2-
ester, SiO-CH3, C3P=0
substituted aromatic,
fused rings
3,400
3,050
2,920
1,620
1,600
1,460-1,430
1,380
1,300
1,260
1,240
840-700
740
W
M
W
M
M
M(multiplets)
W
VW
W
W
S(multiplets)
S
OH, NH
unsaturated CH
saturated CH
C=C, N-C=N
aromatic ring
CH2 , CH3, CH2Cl
SCH3 , SCH2
CH3
S-CH3
CH2C£
S-CH2
aromatic ring, fused
rings, substituted pyridine
C-C£
ro
ro
-------
TABLE 8. ORGANIC CATEGORIES IN SASS SAMPLES
3
Concentration(mg/m )
Categories SASS 1 SASS 2
Aliphatic hydrocarbons
Halogenated aromatic HC's
Aromatic HC's-benzene
<216
>216
Heterocyclic N
Heterocyclic S
Heterocyclic 0
Phenols
Esters
Ethers
Amines
Amides
Car boxy lie acids
Sulfonic acids, sulf oxides
Sulfur
Inorganics
Unclassified
Slli cones
1.1
-
0.6
28.7
25.6
20.1
2.4
2.2
0.2
0.5
-
-
-
0.6
-
0.2
0.1
0.3
0.1
1.1
-
0.1
28.2
28.7
24.0
2.5
6.7
0.3
0.2
-
-
-
0.7
-
0.7
-
1
-
23
-------
ARSENIC, MERCURY, AND ANTIMONY COMPARISONS
Arsenic, mercury, and antimony are determined by atomic absorption in
the Level 1 procedures. Table 9 compared the levels of these elements found
in the impinger solutions from the two SASS's. The estimates of precision
of analysis were provided by Arthur D. Little, Inc. The agreement appears
reasonable, based on the precision estimates for As and Sb. However, the
difference in the Hg concentrations, although less than a factor of two, is
larger than would be expected from analysis imprecision alone.
24
-------
TABLE 9. ARSENIC, MERCURY AND ANTIMONY DETERMINATIONS
SASS 1
SASS 2
As -
(Ug/m )
0.83
0.71
Hg 3
(ug/m )
0.40
0.24
Sb 3
(yg/m )
0.10
0.06
ESTIMATED PRECISION OF ANALYSIS
CV(As) = 5%, CV(Hg) = 10%, CV(Sb) = 25%
25
-------
SECTION 5.0
RESULTS OF ANALYTICAL METHODS EVALUATION
Evaluation of Level 1 environmental assessment methodologies for analysis
of SASS samples was performed by providing control samples of three types to
the participating laboratories. The control samples were prepared and
analyzed by Arthur D. Little, Inc. Arthur D. Little's results are used as a
fourth set of data for interlaboratory comparisons. Laboratories or partici-
pants are coded as A, B, C, and D and are not further identified in this
report.
ORGANIC ANALYSIS RESULTS
The order of discussion for organic analyses follows the analytical
scheme presented in Table 2. That order is:
1. TCO + Grav analyses of each of the three samples types.
2. TCO + Grav analyses of the LC fractions.
3. IR analyses of LC fractions.
4. LRMS analyses of LC fractions.
TCO and Grav Analyses of Phase II Samples
The first step in analyzing a Level 1 sample is the determination of
the volatile (TCO) and nonvolatile (Grav) organic contents in the sample.
Tables 10-12 compare the initial TCO and Grav values determined by the four
participants for three aliquots of each of the three sample types. The
three aliquots of the artificial sample in methylene chloride were not
identical and yield interlaboratory comparisons only. However, the aliquots
of the artificial sample on a flyash matrix and of the field sample were
identical and may be compared for intralaboratory repeatability as well.
XAD-2 Extract Results--
Total organic (TCO + Grav) determinations for the field sample (Table
13) show good agreement. The average and coefficient of variation (CV) of
the 12 determinations are 480 mg and 4 percent, respectively. The range for
the 12 values is only 52 mg or 11 percent of the average.
26
-------
TABLE 10. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE IN CH,C19 (rag)
22
A
B
Aliquot 1 _
D
A
B
Aliquot 2 c
D
A
B
Aliquot 3 c
D
TCO
106
100
105 AVG = 97
76 CV = 15%
97
79
92 AVG = 99
129 CV = 21%
143
106
132 AVG = 159
256 CV = 42%
GRAV
121
171
167 AVG = 126
44 CV = 47%
104
146
129 AVG = 108
51 CV = 39%
169
213
248 AVG = 183
100 CV = 35%
TOTAL
227
271
272 AVG = 222
120 CV = 32%
201
225
221 AVG = 207
180 CV = 10%
312
319
380 AVG = 342
356 CV = 9%
to
Known weights of organics:
Aliquot 1 - 246.1 mg/20 ml
Aliquot 2 - 192.0 mg/20 ml
Aliquot 3 - 302.6 mg/20 ml
-------
TABLE 11. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE ON FLYASH MATRIX (mg)
A
B
Aliquot 1 p
D
A
B
Aliquot 2
V*
D
A
B
Aliquot 3 _
D
TCO
71.2
69
144
51
70.3
81
97
12 rag/g
62.5
82
314
12 mg/g
GRAV
67.6
104
69
47
72.0
124
62
12 mg/g
1 73.0
135
51
14 mg/g
TOTAL
139
173
213
98
142
205
159
136
217
365
00
AVG = 104
CV = 75%
AVG
CV
80
37%
AVG
CV
185
40%
-------
TABLE 12. TCO/GRAV RESULTS: FIELD SAMPLE, XAD-2 EXTRACT (mg)
A
B
Aliquot 1 p
D
A
B
Aliquot 2 c
D
A
B
Aliquot 3 c
D
TCO
106
78
88
150
144
64
110
86
*
142
46
118
134
GRAV
386
380
359
340
343
432
366
360
'354
428
380
360
TOTAL
492
458
447
490
487
496
476
446
496
474
498
494
KJ
VO
AVG = 106
CV = 32%
AVG = 374
CV = 8%
AVG = 480
CV = 4%
-------
Determinations of nonvolatile organics showed good interlaboratory
agreement. The average and CV for the 12 values are 374 mg and 8 percent,
respectively.
TCO determinations show within laboratory CV's of 16, 26, 15, and 27
percent for participants A, B, C, and D, respectively. The agreement be-
tween participants A, C, and D is good. Participant B reports an average
value of 63 mg, almost half of what the other participants reported.
Examination of the TCO procedures used revealed that participant B was
operating the GC at a lower injection port temperature than the other
participants were. This may account in part for the lower TCO values
reported. Participant B also interpreted the Grav procedure as being a
single weight. The samples were not taken to dryness, which would account
for higher Grav values. The combination of low TCO's and high Grav's result-
ed in totals which were comparable to those of the other laboratories.
Artificial Sample Results
The artificial samples show greater variation in both the individual
TCO and Grav values and in the totals. Averages and coefficients of varia-
tion are indicated in the tables. In addition, Table 10 for the artificial
sample in methylene chloride gives the known weight of organics for each of
the three aliquots. For this sample, the total (TCO + Grav) weights obtained
by the laboratories are well within the accuracy limits of Level 1.
TCO and Grav Analyses of the LC Fractions
Results of the TCO and Grav analyses of the LC fractions for the three
sample types are given in Tables 13-17. The data show an overlap or "smear-
ing" of fractions, resulting in differences in distribution among the four
contractors. For example, the totals (TCO + Grav) for fraction 2 and for
fraction 3 of the XAD-2 extract (Table 17) show large differences among the
four contractors, whereas the sums of fractions 2 and 3 are fairly consistent.
Observation of the low total Grav value for Lab D as compared to the
other labs and the theoretical total (216 mg) indicates quite different
drying procedures or incomplete stripping of the column. However, the
distribution of TCO values across all LC fractions for Lab D points more
strongly to a drying problem than to column problems. Apparently, more
detailed and specific procedures would improve comparability among labora-
30
-------
TABLE 13. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE IN CH2C12, ALIQUOT 1 (mg)
TCO
A
14.0
15.3
24.6
12.7
11.3
44.3
0.3
3.0
125.5
B
2.6
<0.30
9.6
2.8
1.6
7.6
0.21
<0.30
25.0
C
23.3
10.0
17.2
7.4
2.9
28.0
9.4
N.R.
98.2
D
14
10
5.4
3.1
2.4
18.0
4.5
57.4
A
19.3
0
22.0
3.3
20.0
93.9
0
12.0
170.5
GRAV
B
14.7
1.0
45.2
13.0
18.7
65.1
24.3
15.8
197.8
C
11.
9.
19.
19.
1.
60.
0
0
121.
0
4
0
6
4
2
7 8
3 8
A
33
15
47
16
31
138
0
15
295
TOTAL
B
17
<1
55
16
20
73
25
16
223
C
35
19
37
27
4
89
9
0
220
D
14
10
5
3
2
26
--
5
65
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
TOTAL
*Very low (0.1 mg) gravimetric values that fluctuated with time were not reported by Lab D.
-------
TABLE 14. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE IN CH2C12, ALIQUOT 2 (mg)
TCO
A
12.0
18.0
22.6
17.0
4.7
42.6
2.0
9.3
128.2
B
7.5
<0.30
10
4.1
1.0
5.0
<0.30
<0.30
28.5
C
69.6
17.3
21.4
7.6
17.8
26.1
6.8
N.R.
166.6
0
10
19
17
11
4.0
36
--
3.1
100.1
A
19.3
8.0
24.0
4.0
10.0
38.0
0
5.3
108.6
GRAV
B
16.1
1.7
42
11.6
6.6
40
15.8
16.6
150.4
C
12.
11.
10.
10.
0.
35.
0
0
'80.
0
6 *
3 4.4
3
0
5
9 31
4.4
77
6 116.8
A
31
26
47
21
15
81
2
15
238
TOTAL
B
24
<2
52
16
8
45
16
17
180
C
82
29
32
18
18
62
7
0
248
D
10
23
17
11
4.0
67
4.4
80
216
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
TOTAL
"Very low (0.1 mg) gravimetric values that fluctuated with time were not reported by Lab D.
-------
TABLE 15. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE IN CH2C12, ALIQUOT 3 (mg)
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
TOTAL
A
20.6
10.3
24.6
28.0
11.0
47.0
2.7
0
144.2
TCO
B
9.4
<0.30
3.4
1.9
2.3
11
0.63
<0.30
29.2
C
42.7
6.4
31.6
15.5
1.3
68.3
36.3
N.R.
202.1
0
39
24
15
18
2.3
56
1.2
12
167.5
A
17.6
4.0
24.0
26.0
22.6
79.9
10.0
5.3
189.4
GRAV
B
11.6
3.8
41
18.1
31.2
91
69
15.6
281.3
C
8.1
2.7
30.6
42.7
1.3
93.5
0
0
179
0
*
20
52
40
24
136
A
38
14
49
54
34
127
13
5
334
TOTAL
B
21
4
44
20
34
102
70
16
311
C
51
9
62
58
3
162
36
0
381
0
39
24
15
38
2
108
41
36
303
CO
*Very low (0.1 mg) gravimetric values that fluctuated with time were not reported by Lab D.
-------
TABLE 16. TCO/GRAV RESULTS: ARTIFICIAL SAMPLE ON FLYASH MATRIX, ALIQUOT 1 (mg)
TCO
A
12.3
7.7
14.0
1.7
0.1
21.3
0.7
0
57.8
B
9.4
1.6
3.8
<0.20
<0.20
15
3.4
<0.20
33.8
C
4.9
3.4
2.6
0.3
2.6
11.9
7.0
N.R.
32.7
D
12
20
1.1
1.5
0.13
1.1
0.73
24
60.6
A
21.0
4.0
18.6
8.7
8.7
18.6
2.7
10.7
93.0
GRAV
B
40
4.0
26
8.2
4.8
30
6.8
8.2
128.0
C
6.
2.
9.
9.
4.
6.
0
0
39.
D
5 *
3
9
3
4
7 6.7
0.45
4.4
1 11.6
A
33
12
33
10
9
40
3
11
151
TOTAL
B
49
6
30
8
5
45
10
8
161
C
11
6
12
10
7
19
7
0
72
D
12
20
1
2
0
8
1
28
72
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
TOTAL
to
*Very low (0.1 mg) gravimetric values that fluctuated with time were not reported by Lab D.
-------
TABLE 17. TCO/GRAV RESULTS: FIELD SAMPLE, XAD-2 EXTRACT, RUN 1 (mg)
TCO
A
1.4
15.2
54.7
0.5
0.9
3.2
0.5
0.9
77.3
B
<0.4
<0.4
31
2.3
0.84
1.0
<0.4
<0.4
36.7
C
12.0
60.3
40.3
9.2
0.4
18.4
21.6
N.R.
162.2
0
2.1
120
2.6
1.4
7.4
13
1.9
8.3
156.7
A
11.5
4.6
259.4
10.1
31.3
16.6
2.8
3.7
340
GRAV
B
4.0
6.4
284
22
8.8
38
23
37
423.2
C
4.8
84.2
177.6
12.8
7.6
27.1
3.6
0
317.7
D
*
200
19
110
50
379
A
13
20
314
11
32
20
3
5
418
TOTAL
B
4
7
315
24
10
39
23
37
459
C
17
145
218
22
8
46
25
0
481
0
2
320
22
1
7
123
2
58
535
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
TOTAL
*Very low (0.1 mg) gravimetric values that fluctuated with time were not reported by Lab D.
-------
tories. Such procedures are included in the revised Level 1 Procedures
Manual.
Identification of Functional Groups by IR
Two sets of IR data are presented for each sample type. One set is
presented in Tables 18-20 and represents a listing of the functional groups
identified by three participants in each of the sample types prior to LC
separation. (Lab C did not include total sample IR spectra in the first
report; these data were received later and are included in Appendix H). The
other set of data, given in Appendix E, graphically represent IR results by
LC fraction and participants. Intensity of an IR peak is indicated by the
length of the line, and broad bands are indicated by a horizontal line of
appropriate width. Listings of functional groups identified in each of the
LC fractions are given in Appendix F.
In view of the complexity of the samples before LC fractionation, it is
not surprising that there is not a one-to-one correspondence of spectra in
Tables 18*20. In most cases where a band is identified by only one lab, the
band is of medium or weak intensity.
Examination of the data presented in Appendix E reveals the same type
of fractional overlaps as were noted in the TCO and Grav analyses. In
addition, Laboratories C and D reported a number of bands that are not
reported by Laboratory A or B. Possible explanations are sample contamina-
tion, artifacts from the column, or sensitivity of the IR spectrometer used.
Categories, Subcategories, and Specific Compounds by LRMS
Categories identified in the three sample types by LRMS are shown in
Appendix G by LC fractions. The LC fraction, the category name, and rela-
tive abundances (100, 10, or 1) are given in the table. In many cases,
particularly for Laboratories C and D, the TCO and Grav analyses did not
"trigger" a LRMS analysis. These fractions are indicated by "NR." In
addition, the "trigger" values originally used by Lab C were the Grav values,
only, and these were not calculated back to the source. When the values
were recalculated, a number of fractions triggered a LRMS analysis. Since
the Grav samples had been preserved, it was possible for Lab C to obtain low
resolution mass spectra. These results are included in a separate appendix
(Appendix H).
36
-------
TABLE 18. IR RESULTS: ARTIFICIAL SAMPLE IN CH2CL2, ALIQUOT 1
Functional Group
Lab A
V cm"1
Lab B
V cm'1
Lab D
V cm
OH or NH
Aromatic CH or
alkyl OH
Aliphatic CH
Ester (aldehyde;
saturated ketone)
Acid C=0
Aromatic C=C
(cyclic C=N)
C-N02 (Amide)
CH3 (Arom C=C)
Ester; ether; alcohol
Phenol; acid
Benzene substitution
Alcohol; substituted
aromatic ring
Substituted aromatic
ring
3,300(M)
3,050(M)
2,950, 2,925,
2,850(W)
1,730(S)
1,700(M)
1,600(S); 1,500(M)
1,530(8)
1,450(M)
1,270(8); 1,120(M)
1,230(M)
1,160(W)
1,100-1,OOO(M)
850-700(M)
3,600-2,300(W)
3,100-3,000(M)
3,000-2,800(8)
1,720(M)
1,710(M)
1,600, 1,590,
1,497(M)
'1,530, 1,342(8)
>1,370-1,360(M)
1,270, 1,118(M)
830-680(M)
3,050(W)
2,960, 2,930,
2,850(8)
1,720(M)
1,595, 1,490(M)
1,265(8); 1,195(W)
1,195(W)
815, 775(8)
-------
TABLE 19. IR RESULTS: ARTIFICIAL SAMPLE ON FLYASH MATRIX, ALIQUOT 1
Functional group
Lab AI
V cm
Lab BI
v cm
Lab DI
V cm
00
OH or NH
:H, aromatic or olefinic
Aliphatic CH
Ring vibrations; N-C=N
=0; conjugated or amide I
H3; CH2
IH3
Aromatic alcohols
Aliphatics; primary alcohols;
aromatics
Substituted benzene
3,050, 3,020(M)
2,960, 2,920,
2,850(8)
1,600(M); 1,490(M)
1,460-1,440(M)
1,370, 1,340(M)
750, 690(S)
3,600-2,500(M);
3,500-3,100(M)
3,100-3,000(M)
3,000-2,800(8)
1,590, 1,490(M)
1,690-1,660(W)
1,460, 1,450(M)
<1,370
750, 695(8)
3,400(W)
3,080(W); 3,060(M)
3,020(8)
2,980, 2,950(M)
2,920(8)
1,600(8), 1,495(8)
1,455(8)
1,375, 1,350(H)
1,030(M)
755, 700(8)
-------
TABLE 20. IR RESULTS: FIELD SAMPLE, XAD-2 EXTRACT, RUN 1
u>
vo
Lab Aj Lab B. Lab D.
Functional group V cm v cm" v cm"
OH or NH
Aromatic CH
Aliphatic CH
Combination bands, aromatic
(etone; «-Cl ketone; esters;
aldehydes
C=0, acidic
ting vibrations; N-C=N
CH3; CH2; aromatic CH3; CHgCl
Alkanes; amines; esters; alcohols
Ssters ; ketones
Ssters; phenols; ether
Aromatic substitution
C-C1
3,400(W)
3,050(M)
2,950, 2,930,
2,850(M)
1,730(W)
1,600(M); 1,500(W)
1,460-1, 430 (M)
1,380(W)
1,200(W)
840-700(8),
multiple
740(S)
3,600-3,300(W)
3,100-3,000(8)
3, 000-2, 800 (M)
2,000-1,650(W)
1,710(M)
1,595, 1,495(M)
900-700(8)
3,420(W)
3,050(8)
2,960, 2,920
2,850(M)
1,710(W)
1,600(M)
1,455, 1,440(M)
1,300(W)
1,300(W)
1,240(W)
1,180(W)
865-715(M-S)
multiple
-------
To evaluate the effectiveness of the LRMS trigger, the LC fractions
meeting the weight criterion for LRMS, as well as the LC fractions for which
spectra were actually obtained, are tabulated in Table 21. The largest
discrepancy noted was in the artificial sample in methylene chloride.
Although this sample was judged to be the "simplest," Labs A and B met the
weight criterion on seven of the eight fractions, Lab C on five fractions
(after recalculating back to the source) and Lab D met the criterion on only
one fraction. While fractional overlap could account for some differences
in the number of fractions which trigger a LRMS, it would not account for
the fact that Lab D triggered on only one fraction. As discussed above,
Lab D consistently reported lower gravimetric values than the other labs.
Gravimetric values in the range of the other labs would have resulted in a
LRMS "trigger" in many cases.
A comparison of categories identified by LRMS in the artificial sample
in methylene chloride is given in Table 22. Of a total of thirteen cate-
gories identified by one or more labs, only two categories were identified
by all four labs. The fraction numbers in parentheses indicate that the
laboratory identified the category by IR but not by LRMS. Since Level 1 is
"designed to show within broad general limits the presence or absence, the
approximate concentrations, and the emission rate of inorganic elements,
selected inorganic anions, and classes of organic compounds," these results
fall short of the expectations of a Level 1 analysis. Carelessness early in
the analysis scheme (LC procedures, TCO and Grav procedures) will result in
failure to trigger all the LRMS analyses that should be performed, and
organic category information will be lost.
Subcategories and specific compounds by LC fraction are given in Appen-
dix I. The reporting format for Level 1 indicates that these increasingly
more specific data should be reported where appropriate and if possible to
do so from the spectra. The lack of data from Labs C and D precludes compari-
son of compounds for each of the samples across the four labs. However,
Labs A and B showed a 34% overlap of compounds identified for Sample 1, 21%
for Sample 2, and 34% for Sample 3.
Table 23 lists the known components of the artificial sample in methy-
lene chloride (Sample 1) and indicates in which fraction(s) each was identi-
fied (if at all) by each of the four laboratories. Although Level 1 is not
40
-------
TABLE 21. LC FRACTIONS WHICH TRIGGERED LRMS vs. LRMS OBTAINED
Artificial sample
In MeCl2
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
Artificial sample
on fly ash
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
XAD-2 extract
LCI
LC2
LC3
LC4
LC5
LC6
LC7
LC8
Lab A
>O.S Bg/B3 LRMS
V V
V V
V V
V V
V V
V V
V
V V
V V
V
V V
V
V
V V
V
V
V
V V
V V
V
V V
V V
V
V
Lab B
>0.5 Bg/m3 LRMS
V V
V
V V
V V
V V
V V
V V
V V
V V
V
V V
V
V
V V
V
V
V
V
V V
V V
V
V V
V V
V V
Lab C
>0.5 fflg/a3 LRMS
V
V
V V
V V
V V
V
V
V V
V V
V V
Lab D
>0.5 mg/m3 LRMS
V
V V
V
V V
V.
V
V
V
V V
V V
V V
V V
V V
-------
TABLE 22. CATEGORIES IDENTIFIED BY LRMS IN ARTIFICIAL SAMPLE
IN CH2CL2, ALIQUOT 1
Categories
Aliphatic hydrocarbons
Halogenated aromatic HC's
Fused alt/non-alt HC's
Heterocyclic S compounds
Esters, phthalates
Aromatic HC's, benzenes
Nitro aromatic HC's
Heterocyclic N
Carboxylic acids, derivatives
Ethers
Phenols
Sulfonic acids, sulf oxides
Inorganics
LC fraction(s) in which
Lab A Lab B
1,2 1,2
2
2,3,4,5 3,4,5
2,3,4
4,5,$, 8 (6,7)
3,4,5 3
(4,5) 4,5,6
4,6,7,8
5,6,7,8 4,5,6,7
6,7,8
6,7,8 6
6,7
8
category was
Lab C
(O*
3,4
4,6
3,6
(4,5,6)
6
(6)
identified
Lab D
2
2
2
(2,4,5,6)
6
(2)
(4,5)
6
*Fraction numbers in parentheses indicate that the category was identified by
IR but not by LRMS.
42
-------
TABLE 23. SPECIFIC COMPOUNDS IDENTIFIED BY LRMS IN ARTIFICIAL
SAMPLE IN METHYLENE CHLORIDE, ALIQUOT 1
Composition
Squalane
n-Tridecane
Biphenyl
Chlorobenzene
Acenaphthene
Chrysene
Dihexylether
Dinitrotolurene
Dibenzothiophene
Diethylphthalate
2-Ethylhexanol
Phenol
Quinoline
Palmitic acid
Stearic acid
Di-p-tolylsulf oxide
LC fraction(s)
Lab A
1,2
2,3
2
2,3
2,3,4,5
(7,8)*
4,5
2,3,4
4,6
6
6,7,8
6,7,8
6
6,7
in which category was
Lab B Lab C
1,2
3
3
3,4,5 3,4
4,5,6
(3,4)
6
6
6,7
6,7
(6,7,8)
identified
Lab D
2
(2)
^Fraction numbers in parentheses indicate peaks at the appropriate m/e which
were either unidentified or identified as another compound.
43
-------
designed to identify specific compounds, the results are disappointing in
that Labs C and D each identified only one of the sixteen components.
Categories identified by LRMS in the artificial sample on a flyash
matrix are given in Table 24. Lab C reported no low resolution mass spectra
for this sample. Of a total of seventeen categories identified by one or
more of the remaining labs, only five were identified by all three. These
results are also outside the limits of a Level 1 analysis.
Table 25 lists the components of the artificial sample on a flyash
matrix and indicates in which fraction(s) each was identified (if at all) by
each of the four laboratories. The large number of peaks that were either
unidentified or identified as another compound (indicated by the fraction
numbers in parentheses) points to a possible problem with the interpretation
of the low resolution mass spectra.
INORGANIC ANALYSIS RESULTS
The Phase-II flyash sample aliquots were Parr-bombed in accordance with
Level 1 procedures and sent to independent laboratories for analysis by
spark source mass spectrometry (SSMS), with the exception of the sample from
Laboratory D which was sent directly to the SSMS analyst with no pretreat-
ment. Results are given in Table 28. In most of the cases shown, the high
and low values for a given element differ by a factor greater than 3.
Nickel and beryllium, which have the lowest MATE values of the elements
shown, were found to range from 13 to 380 ppm and from 0.5 to 14 pg/g,
respectively.
The SSMS analyses for Contractors C and D were performed by the same
outside laboratory. However, since Contractor C's sample was Parr-bombed
and Contractor D's was not, this cannot be considered a true intralaboratory
test of the SSMS technique.
Included in the table are values for arsenic and antimony, two of the
elements for which alternate procedures were specified in Level 1. A compari-
son of these SSMS values to the values obtained by the recommended silver
diethyldithiocarbamate (SDDC) method for arsenic and the atomic absorption
method for antimony is given in Table 29. For Sb, the values obtained by AA
are slightly less than those by SSMS in both cases. For arsenic, however,
the differences are much greater with the SDDC value being higher than the
SSMS value in one case and lower in the other.
44
-------
TABLE 24. CATEGORIES IDENTIFIED BY LRMS IN ARTIFICIAL
SAMPLE ON FLYASH MATRIX, ALIQUOT 1
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic HC's
benzene , substituted
benzenes
Halogenated aromatic HC's
Fused alternate, non-
alternate HC's
Heterocyclic N compounds
Ketones
Heterocyclic 0 compounds
Heterocylic S compounds
Esters
Phenols
Amines
Carboxylic acids and
derivatives
Alcohols
Amides
Sulfur
Inorganics
LC fraction(s) in which category was
Lab A Lab. B Lab C
1
1 no LRMS
reported
2,3,4,5 3,4
1,6 1,2
3 3,4,5,6,7
3,4,5,6,7,8 3,4,5,6,7,8
4
4,5
4,5,7,8"
5,6,7,8 6,7
6,7
5,6,7,8
6,7
1,3,4
8
identified
Lab D
1
1,2,3,4
1
2
3,4,5
4
4,6
5
5,6
5,6,8
6,7
6
45
-------
TABLE 25. SPECIFIC COMPOUNDS IDENTIFIED BY LRMS IN ARTIFICIAL
SAMPLE ON FLYASH MATRIX, ALIQUOT 1
Styrene
Biphenyl/acenaphthene
D ipheny Ime thane
Anthracene/phenanthrene
Stilbene/methylenefluorene
Diphenylethane
Me thy 1 enephenanthr ene
Methylphenanthrene
Diphenylpropene/methylstilbene
Diphenylpropane
Phenylnaphthalene
Dime thy Iphenanthrene
Methylphenylindan/
hexahydropyrene
Diphenylbutane
Diphenylthiophene
Methylchrysene
a-Methylstyrene
Cumene
Cumyl alcohol
Acetophenone
Hexachlorobutadiene
Hexa chlo robenzene
Hexachloroethane
Pentachlorobenzene
Phenol
Cresol
Quinoline
Aniline
Indole
Benzole acid
LC fraction(s)
Lab A
3,4,5
3,4 3
3,4,5
(3,
3
3,4,5
(4)
(3,4,5)
4
5
(4,5)
3,6
(4,5)
1
(5)
6
6
3,5,6,8
6,7
4,5
in which category was
Lab B Lab C
(7,8)* no LRMS
reported
,4,5,6,7
3,4
4,5,6,7,8)
(3,4)
(3,4)
(3,4)
(3,4)
(3,4)
(3,4)
(3)
1
1
(3)
6
6
4,5,6,8
4,5
identified
Lab D
2
2
(2)
(2)
(2)
(2)
2
5
3,5
3
*Fraction numbers in parentheses indicate peaks at the appropriate m/e which
were either unidentified or identified as another compound.
46
-------
TABLE 28. SSMS RESULTS:* ARTIFICIAL SAMPLE ON FLYASH MATRIX
(Mg/g)
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Lab A
2.2
4.7
0.48
15
<2.0
<2.1
<1.9
<2.2
0.36
3.1
0.62
<3.6
9.3
1.4
1.4
11
210
0.43
<0.19
<0.53
2.4
3.1
4.1
<1.0
<0.19
1.3
3.3
52
35
MC
Lab B
2.5
5.1
1.8
33
0.95
NR
0.25
7.2
1.1
STD
5.8
1.6
17
0.66
2.2
1.1
5.0
0.91
9.4
4.4
16
3.5
2.5
12
5.4
23
18
~0.5%
1.0
0.54
0.25
6.9
11
STD
14
0.90
8.7
56
300
41
«3,100
Lab C
3
8
8
0.3
NR
<0.2
2
3
<0.4
0.5
0.2
2
0.3
0.9
1
2
0.4
2
0.7
4
5
2
12
19
MC
0.7
<0.1
<0.2
1
2
STD
3
<0.4
7
160
99
38
MC
Lab D
90
75
0.4
24
0.3
<0.2
<0.2
<0.2
<0.2
<0.3
6
<2
3
0.6
8
0.5
12
16
25
6
15
8
27
36
27
170
180
2
2
<1
0.8
5
STD
0.4
1
<0.2
<0.2
<0.2
15
30
47
(continued)
-------
TABLE 28 (continued)
Element Lab A Lab B Lab C Lab D
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium .
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
8.6
150
6.5
59
2.9
6.3
31
41
25
9.1
MC
230
6.9
39
600
MC
930
520
MC
420
MC
MC
MC
MC
210
2.2
1.1
7.5
9.6
41
41
6.0
4.9
21
42
59
2.7
>1%
200
66
58
«1,700
4.0
>1%
a3,200
210
2,400
800
>1%
>1%
>1%
>1%
450
NR
NR
NR
200
0.6G
32
4
2
5
38
2
15
67
41
380
23
MC
470
160
26
MC
9
MC
MC
58
MC
MC
MC
MC
MC
MC
MC
NR
NR
NR
4
0.5
>130
NR
11
5
13
140
12
42
20
120
13
10
100
130
50
290
230
14
>360
^Results are reported as received from the laboratories;
STD = internal standard.
Lab A: MC = major component; elements for which values are not entered
were not reported*
Lab B: All elements for which values are not entered <0.1 ppm weight;
NR = not reported.
Lab C: NR = not reported; all elements not reported <0.1 ppm weight.
Lab D: All elements for which values are not entered were not reported.
48
-------
TABLE 29. COMPARISON OF As AND Sb BY SSMS AND
BY SDDC AND AA, RESPECTIVELY
Lab A
Lab B
Lab C
Lab D
As.
SDDC
100
775
35
Pg/g
SSMS
59
38
140
Sh, 1'p/g
AA SSMS
0.04 2,4
<1 1
<0.05 0.8
-------
In a separate test of the spark source mass spectrometric technique,
RTI sent four audit samples to an outside laboratory for analysis by SSMS.
Two of the samples (Aliquots 1 and 2) were identical and were prepared in a
low organics matrix (Treatment 1); the other two samples, also identical,
were in a high organics matrix (Aliquots 1 and 2 for Treatment 2). Each of
the samples was weighed and ashed using a low temperature asher. It should
be noted that the sample preparation used for this experiment is not the
recommended Level 1 procedure.
The analysis results, as reported by the outside laboratory, are pre-
sented in Table 30 for twelve elements. For each element, treatment, and
aliquot, the mean of three replicate analyses and the standard deviation
about the mean are given along with the known (RTI) value (determined gravi-
metrically during sample preparation) for selected elements.
To summarize the data in Table 30, it is seen that:
a. The treatment effect was significant at the 0.10 or greater level
for 10 of the 12 elements. In general, the low organic (Treat-
ment 1) sample resulted in lower values than the high organic
(Treatment 2) sample.
b. The aliquot effect within treatments was not significant at the
0.10 level for 11 of the 12 elements.
c. Testing the mean values from 12 analyses per element from the
outside laboratory with the RTI value showed the difference to be
not significant at the 0.10 level for 11 of 12 elements.
d. Testing the mean value from 6 analyses of Treatment 1 samples
against the RTI value showed the difference to be not'significant
at the 0.10 level for 10 of the 12 elements.
50
-------
TABLE 30. RESULTS OF TESTS OF SIGNIFICANCE* AND SAMPLE STATISTICS BY ELEMENT
Outside laboratory
Significance tests
Treatment
effect
Element T
V
Cr
Mn
Ni
Cu
Zn
As
Se
Cd
Pb
Th
Sig(
Sig(
N.S.
Sig(
Sig(
Sig(
Sig(
Sig(
N.S.
Sig(
Sig(
.05)
.05)
.10)
.10)
.10)
.05)
.10)
.01)
.10)
Significance test
Aliquot(T) Mean values (pg/g) outside lab vs. RTI Significance test,
effect (std. deviation, (Jg/g) (combined treatments^) outside lab, vs. RTI
A
N.S
Sig(.OS)
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
Tl Alt
107
(67)
425
(104)
252
(105)
52
(24)
66
>(37)
98
(59)
15
(3)
10
(6)
14
(9)
39
(3)
6
(3)
Tl A2
88
(24)
254
(77)
145
(25)
41
(2)
63
(1)
101
(9)
20
(3)
11
(3)
11
(3)
47
(6)
10
(0)
T2 Al
166
(28)
299
(73)
221
(61)
71
(9)
96
(32)
193
(93)
33
(9)
19
(2)
21
(24)
73
(8)
5
(5)
T2 A2
156
(46)
172
(27)
269
(114)
71
(38)
134
(60)
145
(29)
37
(16)
13
(4)
7
(4)
57
(15)
3
(2)
N.S.
Sig(.lO)
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
RTI(Mg/g)
107
66
247
49
64
145
31
5
.7
35
12
(treatment 1 only§)
N.
S.
Sig(.lO)
N.
N.
N.
N.
S.
S.
S.
S.
Sig.(.OS)
N.
N.
N.
S.
S.
S.
N.S.
See footnotes at end of table.
(continued)
-------
TABLE 30 (con.)
Outside laboratory
Significance tests
Treatment Aliquot(T) Mean values(pg/g)
effect effect (std. deviation, Mg/g)
Significance test
outside lab vs. RTI
(combined treatments^)
Significance test,
outisde lab, vs. RTI
Element
U
T A
Sig(.lO) N.S.
Tl Alt
6
(3)
Tl A2
10
(0)
12 Al
6
(A)
T2 A2
3 N.S.
(2)
RTI (Mg/g)
6
(treatment 1
N.S.
only§)
*Sig.(.10) = significant at 0.10 level,
Sig.(.OS) = significant at 0.05 level,
Sig.(.Ol) = significant at 0.01 level,
N.S. = not significant.
tTl Al = treatment 1, aliquot 1, etc.
^Combined treatments 1 and 2; tested RTI's one value versus mean of 12 outside laboratory values
(i.e., overtreatment and aliquot).
§Treatment 1 only; tested RTI's one value versus mean of 6 outisde laboratory values (i.e., over
aliquots for treatment 1 only).
-------
REFERENCES
1. U.S. Environmental Protection Agency, IERL-RTP Procedures Manual:
Level 1 Environmental Assessment, EPA-600/2-76-l60a, U.S. Environmental
Protection Agency, Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina 27711 (June 1976).
2. "Method 1Sample and Velocity Traverses for Stationary Sources,"
Federal Register. Volume 42, No. 160 (Thursday, August 18, 1977) p.
41755.
3. "Method 5Determination of Particulate Emissions from Stationary
Sources," Federal Register, Volume 42, No. 160 (Thursday, August 18,
1977), p. 41776.
4. Dixon, W. J., and F. J. Massey, Jr. "Introduction to Statistical
Analysis," Chapter 10, 2nd- ed., McGraw-Hill Book Company, Inc., New
York, N.Y. (1957).
53
-------
APPENDIX A
COMPOSITION OF
PHASE II
ARTIFICIAL SAMPLES
54
-------
TABLE A-l. ARTIFICIAL SAMPLES IN METHYLENE CHLORIDE
Composition - mg/20 mis
Squalane
n-Tridecane
Biphenyl
Chlorobenzene
Acenaphthene
Chrysene
Dihexylether
Cn
01 Dinitrotoluene
*Dibenzothiophene
Diethylphthalate
2-Ethylhexanol
Phenol
Quinoline
Palmitic acid
Stearic acid
**Di-p-tolylsulf oxide
Total
Sample Nos. 1*6
(79347-161)
12.7
14.4
13.6
20.1
14.0
15.7
17.8
20.1
12.7
14.4
15.4
16.7
12.6
13.3
12.2
20.4
246.1
Sample Nos. 7-12
(79734-162)
12.7
8.6
13.6
12.1
14.0
9.4
17.8
12.1
12.7
8.6
15.4
10.0
12.6
8.0
12.2
12.2
192.0
Sample Nos. 13-18
(79347-163)
7.6
14.4
13.6
40.2
8.4
15.7
17.8
40.2
7.6
14.4
15.4
33.4
7.6
13.3
12.2
40.8
302.6
* Dibenzofuran was not available in stock.
** p-Toluene sulfonic acid has insufficient solubility for preparation of these samples.
-------
TABLE A-2. ARTIFICIAL SAMPLES ON FLYASH MATRIX
Samples Nos. 19-35
Each sample contains about 5 g of flyash dosed at a level (per 5 g) of:
50 mg Styrene waste - mixture of aromatic hydrocarbons
53 mg API waste extract mixture of aliphatic unsaturated hydrocarbons
and aromatic hydrocarbons
50 mg Lucidol waste - mixture of a-methylstyrene, curaene, cumyl
alcohol, and acetophenone
50 mg Perchloroethylene waste - hexachlorobutadiene, hexachlorobenzene, and a
mixture of other chlorinated hydrocarbons
56 mg Simulated coke waste extract - mixture of phenol, cresol, amines and benzole
acid
25 mg p-Toluene sulfonic acid
More detailed descriptions of the wastes are attached.
(continued)
-------
TABLE A-2. (continued)
Styrene waste extract composition
Styrene
Bipheny1/acenapthene
Diphenylmethane
Anthracene/phenanthrene
Stilbene/methylfluorene
Diphenylethane
Methylenephenanthrene
Methylphenanthrene
Diphenylpropene/methylstilbene
Diphenylpropane
Phenylnapthalene
DimethyIphenanthrene
Methylphenylindan/hexahydropyrene
Diphenylbutane
Diphenylthiophene
Methyl chrysene
- 98.6% soluble
1.8%
6.0%
5.5% .
21.8%
15.5%
10.4%
2.5%
1.8%
7.6%
7.3%
3.5%
1.1%
1.8%
2.9%
1.1%
1.6%
92.2%
(continued)
57
-------
TABLE A-2. (continued)
API waste extract composition
Aliphatics
2n + 3
2n
2n - 2
2n - 4
2n - 6
2n - 8
2n - 10
Aromatics
Aromatics
Aromatics
7.7%
9.3
6.5
4.1
6.3
4.8
4.0
MW <178
MW >178
<216
MW >216
13% soluble
42.7%
14.1%
24%
6.3%
87%
(continued)
58
-------
TABLE A-2. (continued)
Cumene peroxide waste
40% o-Methylstyrene
32% Cumene
18% Cumyl alcohol
3% Acetophenone
0.3% Water
"lucidol waste"
Perchloroethylene waste composition
Hexachlorobutadiene 65%
Hexa chlo robenzene 6.5%
Hexachloroethane 1%
Pentachlorobenzene 2.5%
Others at 1-5%; all chlorinated
(continued)
59
-------
TABLE A-2. (continued)
Simulated coke plant waste
mg Taken for % Abundance
Component simulated waste in real waste
Phenol 640 60
o-Cresol 253 27
Quinoline 91 5
Aniline 72 4
Indole 55 5
Benzole acid 10 <1
60
-------
APPENDIX B
PHASE I INFRARED SPECTROSCOPY RESULTS:
FUNCTIONAL GROUPS IDENTIFIED
IN LIQUID CHROMATOGRAPHY
FRACTIONS
61
-------
TABLE B-l. FUNCTIONAL GROUPS IN CYCLONE EXTRACT LC FRACTION IDENTIFIED BY IR
LC
1
2
3
SASS 1
v, cm *
3,400
2,950, 2,920
2,850
1,460
1,380
3,400
2,950, 2,920
2,850
1,450
1,380
3,050
2,920
1,600
1,460-1,440
1,260
900-700
Intensity
W
S
M
M
M
M
S
M
W
M
M
W
M
M
M
S
Assignment
OH, NH
Aliphatic C-H
CH2
CH2 , CH3
CH3
OH, NH
Aliphatic C-H
CH2
CH2 , CH3
CH3
Aromatic C-H
Aliphatic C-H
Ring vibrations
Aromatic C-H
CH2CL, nitroso dimer,
C-0-N02, S-CH2,
SiCH3
Substituted aromatic,
fused rings
SASS 2
v, cm *
3,400
2,920
1,460
1,375
1,050
3,400
2,920
1,000
t
3,050
2,920
1,930
1,600
1,450
850-700
Intensity
W(broad)
S
M
M
W(broad)
W(broad)
W
S
M
VW
W
M
M
S
(multiplets)
Assignment
OH, NH
Aliphatic C-H
CH2
CH3
C-OH
OH, NH
Aliphatic C-H
Silica gel
Unsaturated CH
Saturated CH
Allene
Aromatic ring
CH2
Aromatic fused
rings, substituted
pyridine
K>
(continued)
-------
TABLE B-l (continued)
LC
4
5
SASS 1
v, cm"1
3,400
3,050
2,920
1,600
' 1,450
1,380
1,200
750
3,400
3,050
2,920
2,220
1,700
Intensity
M
M
W
M
M
M
M(broad)
S
W
W
W
W
S
Assignment
OH, NH
Aromatic C-H
Aliphatic C-H
Ring vibrations
Aromatic C-H,
SiCH2
CH3, SiCH=CH2
SiCH2, phenol,
H2C = CHOCH2
Aromatic, fused
ring
OH, NH
Aromatic C-H
Aliphatic C-H
CHN
Cyclic imide, imide,
carbamate, aromatic
aldehyde, conjugated
ketone, unsubsti-
tuted amidine, HCL
SASS 2
v, cm l
3,400
3,050
2,920
1,700
1,600
1,450
1,050
810-750
3,400
3,050
2,920
2,220
1,930
1,700
Intensity
M(broad)
M
W
M
M
M
M(broad)
M-S
(multiplets)
M(broad)
M
M
W
W
S(sharp)
Assignment
OH, NH
Unsaturated CH
Saturated CH
Ketone, ester,
carbamate, imide
Aromatic ring
N-N02
CH2 , CHg
Ester, ether,
alcohol
Substituted aromatic,
fused rings, substi-
tuted pyridine
NH, OH
Unsaturated CH
Saturated CH
CHN
Allene
Imide, carbamate,
lactam, ester, ketone
0\
CO
(continued)
-------
TABLE B-l (continued)
LC
5
6
SASS 1
v, cm *
1,600
1,450
820
750
3,400
3,050
2,950, 2920
2,850
1,720
1,620-1,600
1,450
Intensity
M
M
W
S
W
M
M
M
S
S
M
Assignment
Ring vibrations
Aromatic CH2, CH2
Substituted pyridine
Substituted aromatic,
fused rings
OH, NH
Aromatic C-H
Aliphatic C-H
CH2
Imide, carbamate,
lactone (6-membered) ,
lactam (5-membered) ,
ketone
C=C, ring vibrations
Aromatic C-H, ali-
phatic C-H
SASS 2
v, cm"1
1,600
1,450
1,200-1,000
820
750
3,300
3,05,0
2,920
2,220
1,930
1,700
1,650
1,600
1,450
Intensity
M
M
M(very
broad)
M
S
M(broad)
M
M
W
W
S
S
S
S
Assignment
Aromatic ring
CH2 , CHa
C-0, ester, ether,
alcohol
Substituted aromatic
substituted pyridine
Substituted aromatic,
substituted pyridine,
fused rings
a.
NH, OH, NH4 , C=CH
Unsaturated CH
Saturated CH
CsN
Allene
Ketone, imide, carba-
mate, lactam ester
Amide, ketone 0-N02
0-N=0, C=N
Aromatic ring N-N02
CH2, CH3
ON
(continued)
-------
TABLE B-l (continued)
Ox
cn
LC
>
7
8
SASS 1
v, cm"1
1,300-1,200
750
3,400
3,050-3,020
2,950
1,730
1,630
1,600
1,450
1,380
1,280
750
3,400
2,220
1,620
1,400
1,150
600
Intensity
M(broad)
S
S(broad)
M
M
M
M
M
M
S
M
M
S(broad)
W(broad)
S
W
M
S
Assignment
C-0, ester, ether
Substituted aromatic,
fused rings
OH, NH
Aromatic C-H
Aliphatic C-H
Imide, carbamate,
lactone, lactam,
ketone
C=C, -CH20-NO
Ring vibrations,
CH2ONO
r*u r*\i
Ltl2 » ^"3
SiCH=SiCH3
CH2-CL, SiCH3
Aromatic, fused
rings
OH, NH
CsN
Substituted olefin
Substituted olefin
Possibly tertiary
alcohol
Substituted olefin
SASS 2
v, cm 1 Intensity Assignment
1,250 S Ester, ether, phenol,
alcohol
810 Ml Substituted aromatic
750 S/ substituted pyridine,
fused ring compounds
3,400 S(broad) NH, OH
2,920 W Saturated CH
/
1,620 M C=C, SiCH=CH2
1,380 S(sharp) SiCH=CH2 inorganic-
salt
-------
TABLE B-2. FUNCTIONAL GROUPS IN XAD-2 EXTRACT LC FRACTION IDENTIFIED BY IR
ON
ON
LC
1
2
3
SASS 1
v, cm 1
3,450
2,950, 2,930
1,470
1,390
3,400
3,040
2,930
1,600, 1,500
1,450-1,430
1,380-1,360
1,240
830-700
3,050
2,930
1,600, 1,500
1,450-1,430
830-700
Intensity
VW(broad)
M
W
W
VW(broad)
M
M
M
M
M
S
M
W
W
M
S
Assignment
NH4, OH
Aliphatic CH
Aliphatic CH
Possibly NH4 salt
NH, OH
Aromatic CH
Aliphatic CH
Ring vibrations
Aliphatic CH
Aliphatic CH
Aliphatic CH,
possibly Si
Substituted benzene,
fused ring compounds
Aromatic CH
Aliphatic CH
Ring vibrations
Aliphatic CH
Substituted benzene,
fused rings
SASS 2
v, cm *
2,950, 2,920
2,850
1,450, 1,375
3,050
2,950, 2,920
2,850
1,730
1,100-1,000
900-700
3,400
3,050
2,920
700-900
Intensity
S
S
W
W
M
M
W
W
W
W(broad)
M
W
S
Assignment
Aliphatic C-H
Aliphatic C-H
Aliphatic C-H
Aromatic C-H
Aliphatic C-H
Aliphatic C-H
Ester
Possibly silica,
possibly alcohol
Substituted aromatic
OH, NH
Aromatic C-H
Aliphatic C-H
Substituted aromatic,
fused rings
-------
TABLE B-2 (continued)
LC
4
5
SASS 1
v, cm l
3,400
3,050
2,950-2,920
1,640
1,600, 1,500
1,450
1,330, 1,320
1,240
800-700
3,400
3,050
2,950-2,930
.
2,220
1,700
1,620
1,600, 1,580
1,440
Intensity
S
M
W
M
M
S
M
M
S
M(broad)
M
M
M
S
M
M
M
Assignment
NH
Aromatic CH
Aliphatic CH
C=C
Ring vibrations
,
vO^~ NH
Substituted aromatic
ring
OH, NH
Aromatic C-H
Aliphatic C-H
C=N
C=0 (ester)
C=C
Ring vibrations
Aliphatic C-H
SASS 2
v, cm *
3,410
3,600-3,200
3,050
2,950-2,850
900-700
i
3,400
3,050
2,950-2,850
2,230
1,700
1,600
1,530
1,450, 1,420
1,300-1,050
Intensity
M
W(broad)
M
W
S
S(broad)
M
S
M
S
S
M
S
M
Assignment
NH
NH, OH
Aromatic C-H
Aliphatic C-H
Substituted aromatic,
fused rings, possibly
dibenzothiophene
OH, NH
Aromatic C-H
Aliphatic C-H
C=N or C=C
Ketone, carboxyl
Conjugated C=C,
a roma tic C=C ,
cyclic C=N, N-N02,
C-N=0, carboxylate
ion
C=N, C-N02
CH3, NH4
Multiple peaks,
alcohol , phenol ,
ester, amines,
C-CL, C=S, Si-O-Si, C-F
(routi nued)
-------
TABLE B-2 (continued)
LC
5
6
7
SASS 1
v, cm l
1,200-1,000
750
3,400-3,300
3,050
2,950-2,930
1,780, 1,720
1,600
1,450
1,380
1,300-1,200
750, 710
3,400
2,950-2,930
1,630
1,600
1,550
Intensity
M(broad)
S
M(broad)
M
M
S
M
M
M
M
M
S(broad)
M
S
S
S
Assignment
C-0 (ester)
Aromatic ring
OH, NH
Aromatic C-H
Aliphatic C-H
C=0 (ketone)
Ring vibrations
Aromatic and ali-
phatic, C-H
o
H
Possibly CH3C-
-c
Aromatic ring
H20, OH
Aliphatic C-H
C=C , amide
Aromatic ring
Amide, CH2-N02
SASS 2
v, cm"1
850-700
3,300
3,050
2,950-2,850
1,780
1,720
1,600
1,530
1,450, 1,420
i
1,270, 1,230
1,100
750, 720
3,400
2,950-2,850
1,730, 1,710
1,630
1,450
Intensity
S
M(broad)
W
M
W
S
S
M
S
S
S(broad)
S
S(broad)
W
M
M
M
Assignment
Substituted aroma tics
OH, NH
Aromatic C-H
Aliphatic C-H
Anhydrides, peroxide,
ester, lactones
Ketone, ester
C=C, C=N, N-N02,
C-N=0, C02
C=N, C-N02
ru uu
U13, NH4
Ester, alcohol,
amine, amide, S03R,
P=0
Alcohol, ether, phos-
phate, silicate
Substituted aromatics
OH, NH
Aliphatic C-H
Ester, ketone, acid
C=C, N-C=N, C=N,
SiCH=CH2
f*Tt pit
Ifii2 ) 1*13
oo
-------
TABLE B-2 (continued)
LC
7
8
SASS 1
v, cm 1 Intensity
1,420 S
1,380 S(Sh)
1,060 M
3,200 S (broad)
1,400 S
Assignment
Aliphatic C-H
SiCH=CH2, inorganic
Salt, CH2-N02
C-0 (alcohol)
NH4
NH4 salt
SASS 2
v, cm * Intensity
1,380 M
1,250, 1,220 S
1,100 W
1,000, 980 M
810 M
,
Assignment
CH3, jl=N, SiCH-CH2
o o
CH2CL, CH2BR, CH2S,
phenol, a, «,
unsaturated ester
2° alcohol, S04
SiCH=CH2, SiC2H5,
CH2= CH-
Melamine, CH2-0-CH=
CH2 , R2C CHR
VO
-------
TABLE B-3. FUNCTIONAL GROUPS IN SORBENT MODULE RINSE LC FRACTION IDENTIFIED BY IR
LC
1
2
3
SASS 1
v, cm l
3,400
2,950, 2,920
2,850
1,100-1,000
3,400
2,950, 2,850
1,100-1,000
3,400
3,050
2,950, 2,850
1,930
1,730
Intensity
S(broad)
S
S
W(broad)
W
S
W
M
M
W
M
Assignment
OH
Aliphatic C-H
Unas signed
Si-O-Si (silica
gel)
OH
Aliphatic C-H
Si-O-Si (silica
gel)
OH, NH
Aromatic C-H, C=C
Aliphatic C-H
Allene
Ester, OfCL ketone,
lactam, olefin,
diketone, aromatic
olefin, C=N, N=N,
N-N02, C-N=0
SASS 2
v, cm'1
3,400
2,920
1,620
1,450
1,380
1,100-1,000
700
3,400
2,920
1,640
1,380
650
3,050
2,920
Intensity
M-S(broad)
S
W
M
M
S(broad)
VW
S(broad)
M
M
M
M(broad)
S
M
Assignment
OH, NH
Saturated C-H
C=C, 0-N02,
C-N=0, amine salt
CH2 , CH3
CH3, H2C=CSi
Si-CH3, SiOSi
CH2-NH-CH2
OH, NH
Saturated C-H
Ketone, C=C, C-NO
CH3
C=C, C-CL
Unsaturated CH
Saturated CH
vj
o
(continued)
-------
TABLE B-3 (continued)
SASS 1
LC v, cm"1
3
1,460-1,420
1,380, 1,310,
1,300
1,240, 1180,
1,130
1,170, 1030
900-700
4
3,050
2,920
1,930
Intensity
M(multiplets)
W
W
W
S
M
W
W
Assignment
J.
CH3, N-N=0, NH4 ,
aromatic C=C
Sharp peaks
Sharp peaks
Ester, alcohol,
ether
Ring substitution,
C-C1
Aromatic C-H
Aliphatic C-H
Allene, substituted
aromatic
SASS 2
v, cm l Intensity
1,620 M
1,600, 1,500 M
1,500-1,400 S
(multiplets)
850-700 S
(multiplets)
620 M
3,450 W
3,050 M
2,930 W
Assignment
C=C, N-C=N
Aromatic ring
S-CH=CH2 , CHs,
CH2 , S-CH2 , S-CH3,
P-CH2, Si -
-------
TABLE B-3 (continued)
^J
ro
LC
4
5
SASS 1
v, cm *
1,600
1,480-1,420
1,260-1,130
1,100
850-700
615
3,400
3,040
2,920
1,930
1,600
1,480-1,420
Intensity
M
M(SH)
M
(multiplets)
M(broad)
S (multiplets)
M
W
M
W
W
M
M(SH)
Assignment
Ring vibrations,
C=C
CH2, S-CH3, N-N=0,
aromatic C=C, C=C
Carbon skeleton
C-0, ether, C-N-C
Aromatic , fused
rings
Biphenyls , naphtha-
lene, ether
OH, NH
Aromatic C-H
Aliphatic C-H
Allene, substituted
aromatics
Ring vibrations,
C=C
CH2 i S CH3 , N N 0,
aromatic C=C, C=C
SASS 2
v, cm l
1,600, 1,500
1,470-1,420
860-700
3,400
3,050
2,920
2,200
1,700
1,600, 1,500
1,450, 1,420
Intensity
M
M
(multiplets)
S
W
M
W
W
M
M
M
Assignment
Aromatic ring
S~CH=CH2 , CH3 ,
CH2 > S-CH2, S-CH3,
P-CH2 Si-
substituted pyridine
Substituted aromatic
rings, fused aromatic
rings, substituted
pyridine
OH, NH
Aromatic and unsatu-
rated CH
Saturated C-H
C=N
Ketone, carbamate,
imide
Aromatic ring
CH2, nitrosamine,
CH3
(continued)
-------
TABLE B-3 (continued)
LC
5
6
SASS 1
v, cm"1
1,260-1,120
840-700
615
3,400
3,050
2,950-2,920
1,710
1,600
1,450
Intensity
M(SH, multi-
plets)
S(multiplets)
M
M(broad)
M
M
S
S
M
Assignment
Carbon skeleton
Aromatic , fused
rings
Biphenyls,
naphthalenes
NH, OH
Aromatic C-H
Aliphatic C-H
C=0, aCL ketone,
dialkyl-ketone ,
conjugated ester,
esters, lactone,
lactam, carbamate,
imide
Ring vibrations, C=C
CH3, CH2, CH2BR
SASS 2
v, cm l
850-700
3,400
3,050
2,920
1,770
t
1,710
1,670
1,600
1,440
1,400-1,200
Intensity
S(multiplets)
S(broad)
M
M
W
S
M
S
M
M(broad)
Assignment
Substituted aromatics,
fused ring compounds
NH, OH
Unsaturated C-H
Saturated C-H
Lactone, imide,
ester
Imide, ketone,
ester
Ketone, lactam, C=C
Aromatic ring, C-N=0
N-N02 , boron compound
CH2 , CHs
Ether, ester, acid,
alcohol, boron
compound
(conLi nued)
-------
TABLE B-3 (continued)
LC
7
8
SASS 1
v, cm'1 Intensity Assignment
1,230 S (broad) C-0, conjugated
ester, CH2-BR,
nitroso dimer,
S-CH2
1,080 S(broad) C-0, conjugated
ester, alcohol,
ether, C-N-C
740 S Cyclic C-CL, NH,
substituted aro-
matic, substituted
pyridine
3,400 S (broad) OH, NH
1,625, 1,600 S, S Unsubstituted amide
1,400 W(broad) C-N
SASS 2
v, cm 1
750
3,400
1,700
1,620
1,600
1,400
1,080
3,400
1,600
1,380
Intensity
S
S (broad)
W
S
S
M
M(sharp)
S
S
S
Assignment
Substituted aromatic,
C-CL, substituted
pyridine
OH, NH
Ketone. imide,
C(NH2)2 CL-,
carbamate
Amide, C=C
Amide, amine salt,
C-N=0, SiCH=CH2
C=C, SiCH=CH2
Unassigned
NH
NH4-CL
NH4-CL
-------
APPENDIX C
CATEGORIES IDENTIFIED IN
PHASE I ORGANIC "EXTRACTS
BY LRMS
75
-------
TABLE C. CATEGORIES IDENTIFIED IN ORGANIC EXTRACTS BY LRMS
a. Cyclone Extracts
SASS 1
LC
LC
>.
LC
LC
Intensity
3 100
10
6 100
100
1
1
Category
Fused alt/non-alt hydrocarbons
Heterocyclic sulfur compounds
Heterocyclic nitrogen compounds
Esters
Carboxylic acids
Phenols
MW Range
128-550
184-234
179-320
390
122
94-108
XAD-2 Extracts
SASS 1
Intensity
1 NR
2 100
100
10
1
Category
i
Fused alt/nonhydrocarbons
Fused alt/non-alt hydrocarbons
Aromatic hydrocarbons
Heterocyclic sulfur compounds
MW Range
<216
>216
SASS 2
Intensity
100
100
1
Category
Fused alt/non-alt hydrocarbons
Heterocyclic nitrogen compounds
Carboxylic acids
MW Range
128-500
129>300
122
SASS 2
Intensity
100
10
100
100
10
10
Category
Sulfur
Aliphatic hydrocarbons
Fused alt/nonhydrocarbons
Fused alt/nonhydrocarbons
Aromatic hydrocarbons
Heterocyclic sulfur compounds
MW Range
256
to 400
<216
>216
92-120
184-198
(continued)
-------
TABLE C (continued)
b. XAD-2 Extracts (con.)
Intensity
LC 3 100
100
10
10
LC 4 100
100
10
LC 6 100
100
100
100
10
SASS 1
Category
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Aromatic hydrocarbons
Heterocyclic sulfur compounds
Heterocyclic nitrogen compounds
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Unidentified
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Carboxylic acids
Phenols
MW Range
<216
>216
92-168
184, 234
167-267
<216
>216
200-304
179
180
122
94-122
LC 7 NR
SASS 2
Intensity
100
100
10
100
100
100
10
100
100
100
10
10
100
100
100
1
Category
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic sulfur compounds
Heterocyclic nitrogen compounds
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic sulfur compounds
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Carboxylic acids
Phenols
Esters
Carboxylic acids
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Phenols
MW Range
<216
>216
184, 234
167-217
<216
>216
234
167-253
180-208
122
94-108
122
129-253
180
(continued)
-------
TABLE C (continued)
c. Sorbent Module Rinses
LC
LC
LC
LC
LC
Intensity
SASS 1
Category
MW Range
1 Nothing detectable
2 10
1
1
1
3 100
100
10
4 100
100
10
10
1
5 100
100
10
10
1
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Carboxylic acids
Esters
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic sulfur compounds
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Sulfur
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Sulfur
<216
>216
256-284
t
<216
>216
184-234
<216
>216
167
184-234
256
<216
>216
167
184, 234
76, 256
SASS 2
Intensity Category
Nothing
Nothing
100
100
10
1
100
100
10
10
1
1
100
100
10
10
10
detectable
detectable
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic sulfur compounds
Sulfur
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Sulfur
Phenol
Fused alt/non-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Heterocyclic oxygen compounds
MW Range
<216
>216
234
256
<216
>216
167
184
256
94
<216
>216
167-217
184-234
230
-J
00
(continued)
-------
TABLE C (continued)
c. Sorbent Module Rinses (con.)
LC
LC
LC
Intensity
6 100
100
100
100
10
7 100
8 m
SASS
Category
1
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Fused alt/non-alt
Fused alt/non-alt
Carboxylic acids
hydrocarbons
hydrocarbons
Heterocyclic nitrogen compounds
MW Range
153-253
180-280
<216
>216
122
129-253
SASS 2
Intensity
10
10
100
10
10
10
1
1
1
Category
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Heterocyclic nitrogen compounds
Heterocyclic oxygen compounds
Heterocyclic nitrogen compounds
Fused alt/iron-alt hydrocarbons
Fused alt/non-alt hydrocarbons
Heterocyclic oxygen compounds
Phenols
MW Range
179-253
180-280
129-303
180-304
129-179
>216
<216
180-230
186
-------
APPENDIX D
SUBCATEGORIES, SPECIFIC COMPOUNDS
IDENTIFIED IN PHASE 1 ORGANIC
EXTRACTS BY LRMS
80
-------
TABLE D-l. SUBCATEGORIES, SPECIFIC COMPOUNDS IDENTIFIED IN ORGANIC EXTRACTS BY LRMS
(Cyclone Extracts)
JC Subcategories , specific compound
3 Dibenzopyrenes , etc.
Methyl dibenzanthracenes , etc.
Dibenzanthracenes , etc .
Benzoperylene, etc.
Benzpyrenes, etc.
Methylbenzanthracenes
Naphthobenzthiophene
Chrysene, benzanthracenes , etc.
Unidentified
Benzofluorene
Pyrene, etc.
Methyl anthracene/phenanthrene
Dibenzthiophene
Anthracene/phenanthrene
Biphenyl/acenaphthene
Alkyl naphthalenes
Naphthalene
Unidentified PAH
Unidentified PAH
Unidentified PAH
6 Dioctylphthalate
Unidentified
Anthraquinoline, etc.
Unidentified
m/e
302
292
278
276
252
242
234
228
218
216
202
192
184
178
154
142-170
128
200-550
258-302
300-452
390
253
229
203
Composition
^24^14
C23H16
C22H14
C22H12
C2oHi2
C19H14
C16H10S
C18H12
C17H14
C17H12
CieHio
,C15H12
C12HgS
C14H10
C12H10
CnHio~Ci3Hi4
C10Hg
C24H38°4
CisHuN
CjyHuN
Ci5H9N
Intensity
SASS 1
_
-
100
100
100
10
10
100
10
10
100
10
10
10
10
10
10
1
10
100
100
100
100
SASS 2
100
10
100
100
100
10
10
100
-
-
100
-
-
10
-
-
-
1
10
_
10
10
10
00
(continued)
-------
TABLE D-l (continued)
aC Subcategories , specific compound
6 Methyl acridine
Acridine
Alkyl quinolines
Quinoline
Benzoic acid
Cresol
Phenol
Unidentifiable peaks
Heterocyclic nitrogen
Unidentified heterocyclic
Unidentified PAH
m/e
193
179
143-171
129
122
108
94
100-200
200-320
to 400
to 520
Composition
"14" 1 1"
Ci3iigN
C i oHgN-C i 2^ i gN
C9H7N
C7Hg02
C7H80
C6H60
Intensity
SASS 1 SASS 2
10 10
100 100
1
1
10 1
1
1
1
10
1
1
00
-------
TABLE D-2. SUBCATEGORIES, SPECIFIC COMPOUNDS IDENTIFIED IN ORGANIC EXTRACTS BY LRMS
(XAD-2 Extract)
LC Subcategories, specific compound
1 Sulfur
Alkanes
Alkenes
2 Benzyl naphthalene
Benzofluorenes
Pyrene, etc.
Methyldibenzthiophene
Methyl anthracene/phenanthrene
Dibenzthiophene
Anthracene/phenanthrene
Alkylbiphenyls/acenaphthenes
Acenaphthene/biphenyl
Naphthalene + alkyl napthalenes
Trimethylbenzenes
Indane/methylstyrene
Xylene
Toluene
Other PAH
Other polycyclics
Alkylated polycyclics
3 Dibenzopyrenes , etc .
Dibenzanthracenes , etc.
Dibenzof luorenes , etc.
Benzpyrenes , etc .
Methyl benzanthracenes
Naphthobenzo thiophene
Chrysene/benzanthracenes
m/e
256
to 400
to 400
218
216
202
198
192
184
178
168, 182
154
128-170
120
118
106
92
206-246
to 300
to 320
302
278
266
252
242
234
228
Composition
S8
to C3()Hg2
to CsoHgo
C17H14
C17H12
CieHio
CiaHjoS
C15H12
Cj2HaS
C14H10
C13H12» C13H14
C12H10
CloHg-Ci3H14
C9H12
CgHio
CgHio
C^Hg
C24Hi4
C22H14
C21H14
C20H12
CigH14
CieHioS
C18H12
Intensity
SASS 1
NR
10
100
100
-
100
1
100
10
100
100
-
-
10
10
10
10
10
-
100
-
10
100
SASS 2
100
10
10
_
10
100
10
10
10
100
10
10
10
10
10
10
10
10
1
_
-
10
10
10
10
100
00
to
(continued)
-------
TABLE D-2 (continued)
iC Subcategories , specific compound
3 Benzofluoranthenes
Benzylnaphthalene, etc.
Benzofluorenes
Pyrene , etc .
Methyl anthracene/phenanthrene
Dibenzthiophene
Anthracene/phenanthrene
Methyl biphenyl/acenaphthene
Fluorene
Acenaphthylene/biphenyl
Acenaphthylene/biphenylene
Naphthalene + alkyl naphthalenes
Xylene
Toluene
Other PAH
Other PAH- like material
Other PAH
4 Dibenzopyrenes
Dibenzanthracenes
Benzoperylene , etc .
Dibenzocarbazole
Benzpyrenes
Methyl chrysene, etc.
Naphthobenzothiophene
Chrysene, benzanthracenes, etc.
m/e Composition
o 1/1 r* u
Z/O "18" 10
O1O f* U
Zlo »J17"14
216 ^17^*12
202 ^i6"io
1 ft O f* U
iyz (->isWi2
i Q /. r* u c
lo*» ^12"18"
m/* IT
L'14'110
168 ^13"12
166 Cj3Hjo
1 c /. P H
IJH 'J12**10
152 C12H8
lOOlC^l ^11/^11
lZo~ 1 DO ^10"8~^12"12
1 A^I f* U
I (JO Lgnio
92 C7H8
to 326
200-336
to 402
1 AO /^ U
jU/ L24'114
278 ^22Hl4
276 ^22^12
t£.7 C U M
/O/ 1>20"13W
252 "2oHi2
f\ j f\ r* if
242 L19"14
o o /. p u o
2J4 L>16**10£x
O O O P VI
Z/o "1 8** 12
Intensity
SASS 1 SASS 2
100
100 10
100 10
100 100
10
1 10
100 100
10 10
10
100 100
10
100 100-10
10
10
10 10
1
1
1 10
1 10
1
10 10
10 10
10
10
10 100
00
(continued)
-------
TABLE D-2 (continued)
[LC Subcategories , specific compound
4 Benzylnaphthalene , etc.
Benzocarbazole
Benzofluorenes
Pyrene, etc.
Methyl phenazine/phenanthroline
Methyl anthracene/phenanthrene
Methyl carbazole
Phenazine/phenanthroline
Anthracene/phenanthrene
Carbazole
Biphenyl/acenaphthrene
Naphthalene + alkylnaphthalenes
Other PAH
Alkyl-substituted polycyclic 331
series
6 Methyl acridine
Fluorenone
Acridine
Carbazole
Benzoic acid
Methyl cresol
Cresol
Phenol
Phthalate, not specifically identi-
fied
Many components, unidentified
Major unidentified peak
Heterocyclic nitrogen compounds
Alkyl-substituted polycyclic
material
Other unidentified material
m/e Composition
218 C17H14
01 "i <> u u
£.11 ^IB"!!"
216 ^17^12
Ort O ^ If
ZUZ "16" 10
194 ^13^10^2
192 C1SH12
mf II U
"13"! I*'
180 Ci2**gN2
i T o r* u
I/O l»i 4** 10
t £.^ f* U \T
ID/ I>i2llgn
154 £12^10
ml C ^ O U f* U
"" 1 DO ^10"8~*"*12"12
200-328
, 346, 360, 374
.
i no P u u
iyj '-'1 4" 11^
1 O /\ /^ U f\
ItSU L>i3ngU
m/v If Vt
^13"9"
i x -i r* u M
ID/ l>}2'*9'*
mf U rt
L>7ngU2
m/^ u /^
ligtl^QU
108 C7H80
94 C6H60
200-304
230
200-300
200-500
200-400
Intensity
SASS 1 SASS 2
10 10
10
10 10
100 100
10
10 10
10 10
10
100 100
100 100
10
10 10
10 10
10
100
100 100
100 100
100
100 100
1
10 10
10 10
10
100
100
10
10
1
00
tn
icon
-------
TABLE D-2 (continued)
LC Subcategories , specific compound
7 Fluorenone
Acridine
Carbazole
Alkylquinolines
Quinoline
Benzoic acid
Methyl cresol
Cresol
Phenol
Unidentified peaks
Unidentified polycyclic material
m/e
180
179
167
143, 157
129
122
122
108
94
135-230
280
Composition
C13H80
C j 3ilgN
C j2"gN
CjoHgN-CuHjjN
C9H7N
C7Hg02
C8H100
C7H80
C6H60
Intensity
SASS 1 SASS 2
NR 100
100
10
10
10
100
1
1
1
100
10
00
NR - Not reported.
-------
TABLE D-3. SUBCATEGORIES, SPECIFIC COMPOUNDS IDENTIFIED IN ORGANIC EXTRACTS BY LRMS
(Sorbent Module Rinse)
JC Subcategories , specific compound
2 Stearic acid
Palmitic acid
Benzpyrenes, etc.
Chrysene, benzanthracenes
Benzofluorenes
Pyrene, etc.
Methyl anthracene/phenanthrene
Anthracene/phenanthrene
Unidentified peak
3 Dibenzopyrenes
Dibenzanthracenes , etc.
Dibenzoperylene/dibenzochrysene
Methylcholanthrene, etc.
Dibenzofluorenes
Sulfur
Benzpyrenes, etc.
Methyl benzanthracenes, etc.
Naphthobenzothiophene/naphtothia-
naphthene
Chrysene, benzanthracenes
Benzyl naphthalene
Benzofluorenes
Pyrene , etc .
Methyl anthracene/phenanthrene
Oibenzthiophene
Anthra cene/phenanthrene
m/e
284
256
252
228
216
202
192
178
326
302
278
276
268
266
256
252
242
234
228
218
216
202
192
184
178
Composition
^18^36^2
C 16^32^2
C20H12
Ci8Hi2
cieHi2
CieHio
cisHi2
Ci4Hjo
C24H14
C22H14
C22H12
C21H16
C2lHl4
S8
C20H12
C19Hi4
CieHioS
C18H12
C17H14
C17H12
CieHio
C15H12
^12^8^
C14H10
Intensity
SASS 1
1
1
1
1
1
10
1
1
1
-
10
10
10
10
-
100
10
10
100
10
100
100
100
10
100
SASS 2
Nothing
detectable
10
10
10
10
10
1
100
10
10
100
100
100
100
100
-
100
00
(continued)
-------
TABLE D-3 (continued)
iC Subcategories , specific compound
3 Biphenyl/acenaphthene
Naphthalene + alkyl naphthalenes
Carbon disulfide
Other PAH
Other PAH
Alkylated polycyclics
4 Dibenzanthracenes , etc .
Benzoperylene, etc.
Sulfur
Benzpyrenes, etc.
Naphthobenzothiophene
Unidentified
Chrysene, benzanthracenes
Benzyl naphthalene
Benzofluorene
Pyrene, etc.
Methyl anthracene/phenanthrene
Dibenzthiophene
Anthracene/phenanthrene
Carbazole
Acenaphthene/biphenyl
Acenaphthylene/biphenylene
Alkyl naphthalenes
Naphthalene + alkyl naphthalenes
Phenol
Carbon disulfide
Unidentified PAH
m/e
154
128-170
76
200-302
to 400
to 430
278
276
256
252
234
232
228
218
216
202
192
184
178
167
154
152
142-170
128-170
94
76
258
Composition
Ci2H10
CioH8-C13H14
CS2
C22H14
C22H12
S8
C2oHi2
C16H10S
ClflHi2
Cl?Hi4
C17H12
CjeHio
C15H12
C i2HgS
C^Hjo
C13H9N
C12H10
CjaHg
CiiHio"Ci3Hj4
CioHa~Ci3Hi4
C6H60
CS2
Intensity
1
SA8S 1 SASS 2
10
10
1
10 10
1 1
1
10
10
1 1
100 10
10 10
10
100 100
100 10
100 10
100 100
100 10
10
100 100
10 10
10
10
10
10
1
1
10
00
00
(continued)
-------
TABLE D-3 (continued)
LC Subcategories , specific compound
4 Unidentified PAH
Unidentified PAH
Alkyl substituted PAH
5 Sulfur
Benzpyrenes, etc.
Methyl chrysene, etc.
Naphthobenzothiophene
Benzanthrone
Anthraquinoline
Chrysene, benzanthracenes
Benzyl naphthalene
Benzocarbazole
Benzofluorenes
Heterocyclic nitrogen
Pyrene, etc.
Methyl anthracene/phenanthrene
Dibenzthiophene
Methyl carbazole
Anthra cene/phenan threne
Carbazole
Carbon disulfide
Other PAH
Other PAH
Alkylated polycyclics
6 Dibenzofluorenone
Benzpyrenes, etc.
Methyl benzanthrone
Benzanthrone
m/e
200-302
200-500
to 566
256
252
242
234
230
229
228
218
217
216
203
202
192
184
181
178
167
76
191-326
128-484
330-468
280
252
244
230
Composition
S8
C2(>Hl2
Ci9H14
CieHioS
C17H100
C17HnN
C18H12
C17H14
CieHuN
C17H12
C15H9N
CieHio
CisH12
Ci2HgS
CisHuN
C14HlO
C^HgN
CS2
C2iH120
^20^12
C18H12°
C17HioO
Intensity
SASS 1
10
1
1
1
100
-
10
-
-
100
-
-
100
-
100
10
10
-
100
10
1
10
-
1
10
10
-
100
SASS 2
1
1
100
10
10
100
100
100
100
10
100
100
100
10
10
10
100
10
-
10
1
-
10
-
10
100
00
VO
(cont in
-------
TABLE D-3 (continued)
iC Subcategories, specific compound
6 Anthraquinoline
Chrysene, benzanthracenes , etc.
Benzyl naphthalene, etc.
Benzocarbazole
Benzofluorenes
Anthraquinone
Pyrene , etc .
Methyl fluorenone
Methyl acridine
Methyl anthracene/phenanthrene
Dibenzthiophene
Fluorenone
Acridine
Anthracene/phenanthrene
Benzoic acid
Other polycyclics
Other polycyclics
7 Anthraquinone
Methyl acridine
Fluorenone
Acridine
Alkyl quinolines
Quinoline
Unidentified heterocyclic nitrogen
compounds
Unidentified heterocyclic oxygen
compounds
Unidentified heterocyclic nitrogen
compounds
Unidentified heterocyclic oxygen
compounds
Unidentified PAH
ra/e
229
228
218
217
216
208
202
194
193
192
184
180
179
178
122
153-278
150-304
208
193
180
179
143-185
129
203-253
204-230
200-303
200-304
202-252
Composition
CiyHuN
CigHia
C17H14
CieHnN
C17H12
C14Hg02
CieHio
Ci4HioN
C14HnN
CisHi2
C^HgS
C13H80
CiaHgN
C14H10
C7Hg02
1
Ci4H802
Ci4Hi1N
Ci3H80
CjsHgN
C10H9N-C13H15N
C9H7N
Intensity
SASS 1
10
100
10
-
10
10
100
10
10
10
10
100
100
100
10
10
1
-
10
-
100
100
100
10
-
1
-
10
SASS 2
_
-
-
10
-
10
-
-
10
-
-
100
100
10
1
1
10
10
100
10
10
10
10
1
1
"
VO
o
(continued)
-------
TABLE D-3 (continued)
LC Subcategories , specific compound
8 Benzanthrone
Chrysene , etc .
Benzyl naphthalene
Benzofluorene
Anthcaquinone
Pyrene, etc.
Methyl fluorene
Biphenol/phenoxyphenol
Fluorene
Acridine
Anthracene/phenanthrene
Methyl quinoline
Quinoline
Unidentified peak
Other unidentified peaks
m/e
230
228
218
216
208
202
194
186
180
179
178
143
129
163
200-260
Composition
C17Hi00
C18H12
C17H14
C17H12
C14H802
C1eH1o
C14H100
C12H10°2
C i sHgO
CjsHgN
C14H10
CioHgN
CgHyN
Intensity
5ASS 1 SASS 2
NR 1
1
1
1
1
10
1
1
1
1
1
10
10
10
1
VO
-------
APPENDIX E
GRAPHICAL REPRESENTATION
OF PHASE II
IR RESULTS
92
-------
IR RESULTS: ARTIFICIAL SAMPLE IN
3500 3OOO 2500 2000 I80O 1600 1400 I2OO IOOO 8OO 600
'll ' I I
-h I ll »
a , ' ' I I I
01 || I II II
3300 3000 25OO 2000 1800 1600 1400 1200 IOOO 800 60O
A2
i i i hhH
82 NOT REPORTED
C2
02 | |
I I I I . . I I II II
I I I I I I I D III I
3500 3000 2900 2000 1800 1600 MOO 1200 IOOO 800 600
» i . n i i H-H
83 , ii i +
C3 I I . I . I , I . 4_, I III
I 0 I I I I II I
3800 3000 2500 2000 1800 1600 MOO 1200 WOO 8OO 600
- + I . + 11
In i I ++ i i il II,, I I hlli I
Mill , II . I I II II I II II I
Figure E-l. IR results: artificial sample in CH2CL2, LC fractions 1-4.
93
-------
IR RESULTS: ARTIFICIAL SAMPLE IN
3500 3000 2500 2000 1800 1600 I4OO 1200 1000 000 600
' i l l I I I i i i i
A5 . +- | I I l I II I
85 + II H
C5 I I I i 11 I l II
05 I I l I
3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600
I I I l l l i i i I l
A6 ,| I I I ,+ I I I
86 H r4f= II III! II , I I H
C6 | || || || I | I || || | ' I III, |
06 l , III I . h I II I III I
3500 3OOO 2500 2000 1800 1600 1400 1200 1000 8OO 600
A7 + || I II , I I II I + + I
87 || I I I I I + I
C7 | I I I l I I I II l l i I ll I II
07 NO IR BANDS
3500 3000 2500 2000 I80O 1600 I4(00 I2OO 1000 800 600
AS I I
88 NOT REPORTED
C8 I I +11, +111. Ill II II
08 NO IR BANDS
Figure E-2. IR results: artificial sample in CH2CL-, LC fractions 5-8.
94
-------
IR RESULTS: ARTIFICIAL SAMPLE ON FLYASH MATRIX
3SOO
3000
Al
Bl
Cl
01
3900
A2
82 NOT REPORTED
C2 i-
02
3000
I
nil
3900
3000
A3
83
C3
03
25oo
2900
2900
H-
il
3900 30fO 2J{00
84
C4
04
i -H-
, nl
i II
ispo iepo
IQjDO 800 600
-
t^^^^^
1 1
>
2000 1800 (600
1 1
I 1..
-1
2OOO 1800 1600
1
1
1
1 1
1
2000 1800 I6OO
1
1 II
, II
1 , 1 1 1 II
1 1 1 >
1400 1200 1000 800
ll 1
1 1
1400 1200 1000 800
1
Mi IM.II II
1
1400 1200 1000 800
1 1 1 1
-^
600
I I
ill H I I -H
Figure E-3. IR results: artificial sample on flyash matrix, LC fractions 1-4.
95
-------
IR RESULTS ARTIFICIAL SAMPLE ON FLYASH MATRIX
3500 3000 25OO 20OO ISOO 1600 1400 1200 1000 800 600
I I I I I I I I I i I
A5 -H HI I ,111 I I
B5 NOT REPORTED
C5
I I I
i
05
AT ,
3500 3000 2500 20OO 1600 1600 1400 I2OO IOOO 800 600
A6
86
C6 , ..,,,,, | | ,
D6 NO IR BANDS
3500 3000 2500 2000 1800 1600 I4OO COO IOOO 800 600
I i l l l l l l I
I I
ll I I II I I I
07 | | I i I I I I I I I I I III
D7 NO IR BANDS
3500 3000 2500 20OO 1800 1600 I4OO COO IOOO 800 6OO
A8 NO BANDS REPORTED
B8 NOT REPORTED
08 III I I I I I I-J I ' I '
08 NO IR BANDS
Figure E-4. IR results: artificial sample on flyash matrix, LC fractions 5-8.
96
-------
IR RESULTS: XAD-Z EXTRACT, FIELD SAMPLE
3900 3000
A.
Bl NOT REPORTED
Cl
Dl
2500
2000 1800 1600 1400 1200
I I
1000
800 600
3900
I
3000
I
A2
B2 NOT REPORTED
II
I I
2900
I
2000
1800 1600 1400
I I T I
1200 1000
I I
BOO
I I + | + I II.
I I II I
600
3900 3000 2900
A3
83
C3
03
f-H
I
2000
1800
1 1
1600 1400 1200 1000
I II
800 600
hHH
i ii ii it 114-
III! IT!
A4
B4
C4
04
2900 2000 1800
' ll ' HII
I I
MOO MOO 1200 1000 800
II II I
' I I II I I
II
++
11
,1
Figure E-5. IR results: XAD-2 extract, field sample, LC fractions 1-4.
97
-------
IR RESULTS: XAD-2 EXTRACT, HELD SAMPLE
3900 3000 2900 2000 1800 1600 I4OO 1200 1000 800 6OO
I I I I I I I I I I I
45 H- 1 II I II I I
B5 , , i
C5 i | | I I I I I I I
I II I I I I I I H- -H I I II I I
05 I III III, ,
3900 3000 2900 2000 1800 1600 I4OO 1200 1000 800 600
I I I I I I I I I I I
A6 l
T III
as, ^H^ iii +
C6 i III
-4- l I I l I I
06 -h III (III
3900 3000
3900 2000 1800 1600 I4OO 1200 1000 800 600
B7
H-
C7 4000U
07 NO IR BANDS
3900 3000 2900 2000 1800 1600 1400 I2p0 1000 800 600
» '+ ' II
68 NOT KtPOHltD
08 | I | | I 1-^ I H- I I I I *+
06
Figure E-6. IR results: XAD-2 extract, field sample, LC fractions 5-8.
98
-------
APPENDIX F
PHASE II
IR RESULTS:
LC FRACTIONS
99
-------
TABLE F-l. IR RESULTS: ARTIFICIAL SAMPLE IN CH2CL2, LC FRACTIONS
LCI
C 2
A
2,920, 2,950
1,460
1,380
3,400
3,050
2,920
1,600, 1,580
1,420
1,300
1,220
1,060
700-850
S
M
M
S (v
broad)
S
S
M
S
(sharp)
M
M
M
S
(mul-
tiple)
saturated CH
CH3, CH2
CH3
OH, NH
unsaturated CH
saturated CH
ring vibrations
CH2 , S-CH3
S-CH3, CH2C£
phenol
alcohol; subs. arom.
subs, arom.; fused
ring compds; C-C£
(740 cm"1)
B
3,000-2,800 S CH, aliphatic
1,460 S CH, aliphatic
1,380, 1,372, M C-CH3
1,360
729, 718 W CH2; -(CH2)n-, N >4
m
o
o
(continued)
-------
TABLE F-l (continued)
LCI
LC 2
C
2,960 S CH2
1,460 S CH3
1 , 380 M isopropyl
1,210 W =CH2 in plane
1,180 W isopropyl
1,150 W -CH=CH2
980-920 W cyclohexane
derivative
730 W -CH3 or C-C£
1,430 M C=CH2
1,310 W C=C trans
1,265 M C-CH2 (possibly in
ring)
1,230 M ^
1,130 W
1,065 W
1,020 W
815 S
755 S
740 S
710 M
700 M
^/
aromatic substitution
y>
D
2,950, 2',930, S aliphatic CH
2,855
1,420 M alkanes
1,375 M alkanes
780, 745 W halogens
3,400 M OH (water)
3,050 M aromatic CH
2,940, 2,920 M aliphatic CH
2,835 W aliphatic CH
1,595, 1,485 M aromatic ring
1,430 S alkenes
1,370 M alkanes, alcohols
1,265 S aromatic ethers
1,075 M alcohols, aromatic
overtones
1,025 S aromatic ether, aro-
matic overtones
870, 860, 780, M aromatic substi-
695 stution
815, 750 S aromatic substi-
tution
(continued)
-------
TABLE F-l (continued)
A
LC3 3,050
2,920
1,600, 1,580
1,420, 1,430
1,260
700-820
LC4 3,400
2,920
1,720
1,600
1,540
1,340
1,000-1,100
810, 740, 760
M unsaturated CH
W saturated CH
M ring vibrations
M aromatic CH, CH2,
CH2C£
M oxirane, CH2C£
S (ami- Subs. arom. or fused
tiple) ring compds.
S(braod) OH, NH
M saturated CH
W dia Iky Ike tone, esters,
imide , ca rbona te
M (some- ring vibrations, C=C
what
broad)
M N02
M aryl NH", N02
M C-0, alcohol, ether,
(broad) ester
M arom. subs., fused
rings, subs, pyridine
B
~3,045 W CH, aromatic
1,590, 1,510 M C=C, aromatic
812, 760-720 S T(CH) , aromatic
3,050 W CH, aromatic
1,610, 1,590, M C=C, aromatic
1,480
1,530, 1,348 M N02
815, 760, 734 S T(CH), aromatic
(continued)
-------
TABLE F-l (continued)
LC3
LC4
C
3,020 M
1,595 M
1,490 W
1,430 M
1,360 W
1,300 M
1,265 Si
1,230 WJ
1,190 W
1,140 W
1,100-950 W
940 W
870, 860 M
815 S
760, 750 S
740 M
710, 700, 690 W
3,050 S
2,960 M)
2,940 M)
1,830 M
1,610 S
1,540-1,510 S
1,490-1,440 S
1,360 M
1,275 M
1,210 M
aromatics
aroma tics
aromatics
C=CH2
C(CH3)x
C=C trans
cyclohexyl
derivative
(possibly pyridine)
aromatics
cyclohexyl derivative
benzene derivatives;
C-CJK at 740
aromatic C-H
|-CH2
aromatic or 0-lactone
aromatic
aromatic or ArN02
-CH2
ArN02
Tert-butyl benzene
D
2,960, 2,930, S aliphatic CH
2,855
1,465, 1,455 M aliphatics
1,375 M alkanes
1,260 M aromatic ethers, esters
1,115 S aliphatic ethers
1,020 M primary alcohols,
aromatic ethers
815, 800 M alkenes
755 W halogen
3,100, 3,050 M aromatic CH
2,960, 2,930, M aliphatic CH
2,855
1,950 W aromatic overtones, C=C=C
1,605 S aromatic ring, amines
1,530 S broad, aromatic ring
1,450, 1,440 W alkanes
1,350 S alcohols
1,265 M aromatic alcohols, aro-
matic ethers, esters
1,205 M aromatic ethers, phenols
1,155 M aliphatic ethers, phenols
amines, aromatic over-
tones
o
to
(continued)
-------
TABLE F-l (continued)
LC4
1
C
1,160 S (CH3)2C
1,075 S \
1,040 S
1,010 W
980 W
aromatic
substitution
920 S CH=CH2
840 S >C=CH2
795 S (CH3)2C
770 M
740 S
715 S
700 M
aromatic
substitution
640 S C-C£
D
1,065, 1,035 M aromatic ethers, aliphatic
alcohols, aromatic over-
tones
915 S alkenes
835, 790, 735, S aromatic subst.
700
625 M alkenes, halogens
3,400, 2,740, weak peaks
1,730, 1,690
(continued)
-------
TABLE F-l (continued)
LC5
r
A
3,400
3,100
1,600
1,530
1,450
1,340
700, 720
630
W
(broad)
M
S
S
W
8
M
M
OH, NH
unsaturated CH
ring vibration
-N02
CH2
-N02
arom. substitution
monoalkyl (benzene,
alkylnaphthalene)
B
3,110-3,030 M CH, aromatic
1,607 S C=C,
1,525, 1,345 S N02
850-700 S T(CH)
aromatic
, aromatic
(continued)
-------
TABLE F-l (continued)
LC5
C
2,960 S CH stretch
1,725 S C=0
1,600 M benzene substitution
1,540 S CN03
1,350 S ArNO or COO or
» V
aldehyde
1,290 S aldehyde, benzoate,
nitroaldehyde or
ketone
1,135-1,110 M PhCOR, phthalate
1,075 M
1,040 W
1,020 W
aromatics
835 W aldehyde, >C=CH
820 M
795 W
760 M
730 W
705 M
aroraatics
680 M C-C£
D
3,100, 3,050 W aromatic CH
2,960, 2,940, W aliphatic CH
2,860
1,600 S aromatic rings, amides
1,525 S aromatic rings, amides
1,380 W alcohols
1,340 S alcohols, amines, amides
1,260 M phenols, esters
915 M alkenes, alcohols,
carboxylic acids
845, 780, 740, M aromatic substitution
730, 700
1,200, 1,150, weak peaks
1,125, 1,070,
1,030
o
o\
(continued)
-------
TABLE F-l (continued)
LC6
A
3,050
2,920
1,730
1,600
1,460
1,380
1,270
1,170
1,010
800
W
S
S
M
M
W
S
(broad)
M
M
M
unsaturated CH
saturated CH
C=0, ester, ketone,
imide, carbamate
ring vibrations
CH2 , CH3 , S-CH2
CH3
CH2C£, C-0, S-CH2,
ether, ester, S-CH3
ester
alcohol, arom. subs.
K2C CHR, S~CH3
B
3,400-2,300
3,300
3,040
3,000-2,800
1,720, 1,700
1,618, 1,602, )
1,590, 1,572,}
1,498 J
1,270, 1,120
1,469
1,362
810-690
1,100
M
M
W
S
S
M
M
M
W
M
OH, acidic
OH, alcoholic
CH, aromatic
CH, aliphatic
C=0, ester and acid
C=C, aromatic
C-O-C, aromatic ester
CH, aliphatic
C-CH3
T(CH), aromatic
minor absorption
maximum
(continued)
-------
TABLE F-l (continued)
c
LC6 2,960 S
1,725 S
1,600, 1,590 W
1,490 M
1,470 M
1,450 W
1,410 W
1,370 M
1,290 S
1,205, 1,175 W
1,125 M
1,085 M
1,075 M
1,045 M
1,020 M
945 Wj
805 M
745 M
720 W
710 W
625 m
C-H stretch
C=0
* aromatic
aromatics (nitro
compound)
-C-CH3
-CH2~possibly in ring
-C=CH2
-C-CH3
C=0
=CH in plane bend,
phthalate, benzoate
=CH in plane bend
8=0 stretch or
phthalate or
cyclohexyl compound
8=0 stretch
8=0 stretch or =CH
in plane bend
acid or cyclohexyl
derivative
aromatics
C-S
D
3,200 W broad, -OH
3,050 W aromatic CH
2,960, 2,920 S aliphatic CH
2,850
1,710 S carbonyls
1,605, 1,590, W aromatic ring
1,500
1,465, 1,455 M aliphatic CH,
(sh) carboxylic acids
1,280 S sulfonic acids, silica
1,070, 1,030 M sulfoxides, aromatic
overtones
805 S aromatic substitution
750, 720, 690 M aromatic substitution
1
630 M S-0
1,410, 1,370, weak peaks
1,225, 1,120,
1,090, 1,010,
940, 780
o
00
(continued)
-------
TABLE F-l (continued)
LC7
A
3,400
2,920, 2,950
1,740
1,700
1,680
1,640
1,580
1,540
1,450, 1,460
1,380
1,250
1,030
720
M
S
H
M
M
W
M
M
M
S
M
(broad)
M
(broad)
W
OH, NH
saturated CH
cyclic ketone, esters
con j . ketone, acid,
iroide, carbamate
ketones, amide
amide, C=C
N02, CHC£N02
C-N=0, N02
CH2 , CHs
CH3, N02
phenol, ether, ester
C-0, alcohol, ether,
subs. arom.
subs. arom.
B
2,910, 2,840
1,722
1,585, 1,488
1,280, 1,115
1,100-1,000
802
M
S
M
S
M
S
CH, aliphatic
C=0, aromatic ester
C=C, aromatic
C-O-C, aromatic ester
C-0
T(CH), aromatic
o
vo
(continued)
-------
TABLE F-l (continued)
LC7
C
2,960 S
1,695 S
1,575 M
1,460 S
1,430 W
1,390 M
1,300 M
1,205 W
1,160 W
1 , 135 W
1,085 Wj
1,040 W
1,010 W'
945 M
820 M
805 W
725 M
685 W
665 W
C-H stretch
C=0: aldehyde, ketone
or acid
coo"
-CH2
acid or aldehyde
>C=CH2
C-0 stretch
=CH in plane bend
aromatics
acid
aromatics
C=C
D
no IR bands
(continued)
-------
TABLE F-l (continued)
LC8
LC8
A
3,100
1,400
ammonium salt
ammonium salt
C
3,450
2,960
1,740-1,680
1,640
1,600
1,560
1,470-1,430
1,420
1,400
1,380
1,350
1,305
1,265
1,225
1,085
1,010
820
750
S
S
M
S
S
W
M
M
M
M
W
M
M
M
M
M J
S
S )
water
C-H stretch
C=0
water
aromatic or COO
aromatic
C-CH3
-C=CH2
-C-(CH3)3
aldehyde or COO*
aldehyde, acid, or
C=C trans
CH2
C-(CH3)3
alcohol, acid or
aromatic
aromatics
B
NR
D
no bands
-------
TABLE F-2. IR RESULTS: ARTIFICIAL SAMPLE ON FLYASH MATRIX, LC FRACTIONS, ALIQUOT 1
Lei
r
tLC 2
1
1
A
2,920, 2,950
1,460
1,340, 1,360
2,920, 2,950
1,450
1,380
S
M
M
S
M
M
aliphatic CH
01₯ Oil
1>H2 , 1>I>3
Off Off
1*113 ^>n2
aliphatic CH
r*u oil
L»n2 ) **"3
CH3
B
3,000-2,800
1,605, 1,560,
1,165
1,460
1,375
1,342, 698
980, 940, 850,
790, 765
720
S
W
M
M
M
M
CH, aliphatic
1,3 hexachlorobutadiene
CH, aliphatic
C-CH
hexachlorobenzene
1 ,3-hexachlorobutadiene
minor absorption
maximum
Not reported
K>
(continued)
-------
TABLE F-2 (continued)
I-"
!"
to
Cl
LC2
C
2,960
2, 000-1, 755 I
1,615-1,540)
1,460
1,380, 1,350
1,300, 1,250,
1,155, 1,150
1,110-910
820, 775, 720,
700
685
3,125-2,815
1,740
1,600
1,575
1,540
1,470
1,450
1,380
805
750
700
S
W
S
M
W
W
W
W
S
W
M)
W
M'
M|
S
M\
Mj
s
si
C-H stretch
.
aromatic
-CH2
-C(CH3)x
aromatics
phosphate
aromatics
C-C2
aromatics
C-H stretch
aromatics
-C(CH3)v
X
aromatics
D
2,955, 2,925,
2,855
1,460
1,375, 1,345,
1,170
980, 940
850
190, 695
650
1,560
3,055, 3,020
2,960, 2,930
2,860
1,600, 1,490
1,450
1,375
755
695
1,025
S
M
W
M
M
W)
Mf
weak
W
S
M
M
M
W
W
S
weak
aliphatic CH
alkanes
alkanes, alkenes
alkanes, alkenes
alkenes
not aromatic
substitution, possible
halogens
peak
aromatic CH
aliphatic CH
aliphatic CH
aromatic ring
aliphatics
aliphatics
aromatic substitution
aromatic substitution
peak
(continued)
-------
TABLE F-2 (continued)
B
(LC3 3,020, 3,060
2,930, 2,950
1,600
1,500
1,450
1,380
700, 750
M unsaturated CH
M saturated CH
M ring vibrations
M ring vibrations
M CH2
M CH3
S subs, aromatic, fused
(sharp) ring compounds
3,100-3,000 M
3,000-2,800 S
2,000-1,600, IS
1,598, l,490j
758, 697 )
1,450 M
1,370 M
735
CH, aromatic or olefinic
CH, aliphatic
raonosubstituted benzene
CH, aliphatic
C-CH3
minor absorption maximum
LC4 3,400
3,030, 3,060,
3,080
2,920
1,600, 1,580,
1,500
1,450
1740
1,000-1,100
750, 700
W OH, NH
(broad)
M unsaturated CH
S
M
saturated CH
ring vibrations
CH2
(sharp)
W cyclic ketone, « CS,
ketone, ester
W C-0, ester, alcohol
(broad)
S subs, arom; fused ring
compounds
3,425 M
3,100-3,000 M
3,000-2,800 S
2,000-1,650, S
1,596, 1,578,
1,489, 740,
697
757
W
NH, secondary amine
CH, aromatic
CH, aliphatic
monosubstituted
benzene
minor absorption maximum
(continued)
-------
TABLE F-2 (continued)
LC3
LC4
C
3,075-2,860 S
1,785 M
1,600 M
1,495 S
1,450 S
1,380 M
1,250-1,225 M
1,200 M>
1,170 W
1,030 M
980, 960 W
910, 860 W
835 W
760 S
750, 745 S
700 -^
3,450 W
3,075, 3,030 M
2,960 S
1,940, 1,905 W
1,785 S
1,600 M
1,515 S
1,460 S
1,410 S
1,390 M
1,370 S
aromatics and C-H
aromatic, >C=CH2
aromatic
aromatic
rCH2- and (CH3)3C
-(CH3)3C
-(CH3)3C
aromatics
OH or NH
aromatics
C-H stretch
aromatics
>C=CH£, acid chloride,
carbonate or lactone
aromatic
aromatic, C-NO , NH4
CIR, NH4C£R,XNH4 +
or phenol
(CH3)v C
>C=CH£
C(CH3)3
C=C (trans)
D
3,060 M aromatic CH
3,025 S aromatic CH
2,925 S aliphatic CH
2,850 W aliphatic CH
1,600 M aromatic ring
1495 S aromatic ring
1,455, 1,375 S aliphatics
1,030 M aromatic overtones
755 S aromatic substitution
695 S aromatic substitution
i
3,050 M aromatic CH
2,925, 2,850 S aliphatic CH
(continued)
-------
TABLE F-2 (continued)
LC4
C
1,340 W
1,315-1,150 S
1,110 M
1,085 S
1,020 S
960, 945 M
895 S
835 S
770-700 S
740 S
700 S
phenols, ethers, or
sulfonic acids
aromatic
sulfonic acid
aroma tics: pyridines,
phenols
>C=CH2, phenols, or
pyridines
aromatics
D
(continued)
-------
TABLE F-2 (continued)
LC5
A
3,400
3,020, 3,050,
3,080
2,920
1,720
1,600
1,500
1,450
700
750
W
(broad)
M
S
W
M
M
M
S
(sharp)
M
OH, NH
unsaturated CH
saturated CH
cyclic ketone, «C£
ketone, ester
ring vibrations
ring vibrations
CH2
arom. or fused rings
subs, arom., fused
rings, C-CS.
B
Not reported
(continued)
-------
TABLE F-2 (continued)
ILC5
C
3,415
3,075
2,960
2,085
1,905
1,770
1,680
1,600
1,505
1,460
1,410, 1,390
1,370
1,225, 1,190
1,165
1,100
1,075
1,015
895
835, 760, 700
W
W
M
W
W
S
W
M
S
M
W
M
S
S
M
M
S
M
Mf
NH or OH
aromatic
C-H stretch
C=C or nitrile
aromatic
C=CH3, carbonate,
acid chloride,
lac tone
aldehyde, ketone, or
acid
aromatic
aromatic, C-NO ,
NH4C£R, NH4+? phenols
C(CHa)3
>C=CH2
C(CH3)3
phenols , ethers ,
sulfonic acids
aromatic
sulfonic acid
pyridines, phenols
C=CH2, phenols
aromatics
D
3,340
3,020
2,960, 2,850
2,920
1,600
1,490
,
1,450
1,260
1,120
1,020
790, '750
695
W
M
M
S
M
M
M
M
W
M
M)
sf
N-H, -OH
aromatic CH
aliphatic CH
aliphatic CH
aromatic ring, amines
aromatic ring
aliphatics
aromatic ethers, COOH
aliphatic ethers,
amines
aromatic overtones,
aromatic ethers,
amines
aromatic
substitution
00
(continued)
-------
TABLE F-2 (continued)
B
3,300
3,020, 3,050
2,920, 2,950
1,720
1,660
1,500
1,450
1,250
1,100
800
750, 700
W NH, C=CH, NH4
(broad)
W
S
M
M
1,600, 1,580 M
M
M
M
M
(broad)
M
S
unsaturated CH
saturated CH
cyclic ketone,
ketone, ester
ketones, mono subs.
amide, C=N, >C=CH,
CH2ONO
ring vibrations
ring vibrations
CH2
ON . .
\N= \-., phenol, arom.
ether, ester, CH2C£,
CH2Br
alcohol, aliphatic
ester, ester
CH2-0-NO
CH2C£, CC£3, cyclic
C-C£, arom. subs, or
fused ring compounds
3,650-2,300 M
3,600-3,000 S
3,100-3,000 M
3,000-2,800 W
1,668 M
1,602, 1,592, ) S
1,498, 1,470,>
753, 690 )
1,3,60, 1,235, )S
1,068, 1,021,}
997, 810, 753J
690
OH, acidic
OH, alcoholic or
phenolic
CH, aromatic
CH, aliphatic
C=0, amide I, or C=C
olefinic
monosubs. benzene
phenol
(continued)
-------
TABLE F-2 (continued)
LC6
C
3,225 M
3,030 M
2,960 S
1,770 W
1,680 W
1,585 S
1,505 S
1,450 M
1,370 W
1,315 W
1,235 S
1,200 M
1,165 W
1,020 W
1,010 W
805 M
750 S
695 8
N-H or OH
aromatic
C-H stretch
C=CH2, acid chloride,
carbonate or lactone
aldehydes, ketone, or
acid
aromatic
aromatic, C-NO , NH4C£
or NH4t, phenols
C(CH3)
C(CH3)3
C=C (trans)
phenols, ethers, or
sulfonic acids
aromatics, especially
pyridines and phenols
aromatics
D
No IR bands
i
NJ
O
(continued)
-------
TABLE F-2 (continued)
LC7
LC8
A
3,400 W OH, NH
2,920, 2,950 W saturated CH
1,730 W cyclic ketone «C£
ketone, ester
1,620 W C=C
1,600 M ring vibrations,
SiCH=CH2
1,380 S SiCH=CH2, inorganic
salt?
1,000-1,100 W C-0
(broad)
690 M subs. atom.
Ammonium salt (chloride)
B
3,600-2,300 M OH, acidic
3,100-3,000 M CH, aromatic
3,000-2,800 M CH, aliphatic
1,600, 1,590,
1,500, 1,360,
1,240, 1,065, S-M phenol
1,020, 995,
803, 750, 695
1,369 M C-CH3
1,720, 1,670, minor absorption maxima
780
Not reported
(continued)
-------
TABLE F-2 (continued)
LC7
to
to
3,335-3,030
2,960
1,770
1,600
1,505
W
W
W
W
W
W
1,450
1,410, 1,235, 1 W
1,190, 1,165/
1,110, 1,075,) W
1,020, 835,[
750, 700 )
NH or OH and aroraatics
C-H stretch
C=CH2, acid Cl,
carbonate or lactone
aromatics
aroraatics, CNO , NH4+
compound or phenols
C(CH3)x
phenols, ethers
sulfonic acids
aromatics
No IR bands
LC8
3,335 W
3,075 W
2,960 W
1,755 W
1,615 W
1,505 W
1,450, 1,420 W
1,280-1,210, \ W
1,205, 1,163?
1,110-700 W
NH or OH
aromatics
C-H
C=0
aromatics
aromatics, C-NO ,
C(CHa)3
phenols and sulfonic
acids
aromatics
No IR bands
-------
TABLE F-3. IR RESULTS: FIELD SAMPLE, XAD-2 EXTRACT, RUN 1, LC FRACTIONS
LCI
LC 2
A
3,400
2,850, 2,920
1,450
1,380
1,070
3,400
3,050
2,850, 2,920
1,600
1,500
1,430-1,450
1,380
1,070
700-860
M
(broad)
S
M
M
S
(broad)
W
(broad)
M
S
M
M
M
M
M
(broad)
M
OH, NH
saturated CH
CH2 , CH3
CH3
SiO-aliphatic,
alcohol, Si-O-Si
OH, NH
unsaturated CH
saturated CH
ring vibrations
ring vibrations
CH2C£, CH2Br, CH2 ,
CH3
CH3
Si-0-aliphatic, Si-O-Si
Subs, arora. or fused
ring compounds
B
Not reported
Not reported
U>
(continued)
-------
TABLE F-3 (continued)
LCI
LC2
C
2,960
1,470
715
3,030
2,960
1,925
1,600
1,505
1,460-1,430
1,370
1,305-1,275
1240
1,200, 1,185
1,165-1,143
1,100
1,040-1,000
980-935
860
840, 815, 780 A
740, 710 [
W
W
W
S
S
M|
S
M)
S
M
W
M
M
W
W
W
M
M
S
C-H
C(CH3)
aromatic
aromatics
C-H stretch
aromatics
C=C
C(CH3)3
C(CH3)3
C-C£
aromatic
aromatics or C(CH3)3
aromatic
aromatics
cyclohexanes
aromatic substitution
C-C£
D
2,950, 2,920
2,850
1,450
1,375
1,530
3,040
2,920
1,600, 1,500
1,455
1,440, 1,430,
1,370
1,240, 1,185
1,140, 1,090
845, 815, 780, \
745, 735, 710J
1,925, 1,670,
1,300, 865
S
W
W
weak
S
M
M
S
W
M
W
S
weak
aliphatic CH
alkanes
alkanes
peak
aromatic CH
aliphatic CH
aromatic ring
alkanes
aliphatics
aromatic overtones
aromatic overtones
aromatic substitution
peaks
10
(continued)
-------
TABLE F-3 (continued)
LC3
LC4
A
3,040
2,920
1,930
1,600, 1,580
1,500
1,450
1,440
1,430
1,300
1,240
1,190
700 (850)
3,400
3,050
2,850, 2,920
1,630
1,600, 1,490
1,450
1,200-1,300
720, 740
S
W
W
(broad)
M
M
(sharp)
S
M
M
M
S (mul-
tiple-
sharp)
S
M
M
M
M
M
M (v
broad)
S
(sharp)
unsaturated CH
saturated CH
alkene
ring vibrations
ring vibrations
CH2 , CH3
S-CH3
aromatic CH
S-CH3
S-CH2
subs. arom.
Subs, aromatic or fused
ring compounds , subs .
pyridines
NH, OH
unsaturated CH
saturated CH
C=C
ring vibrations
CH2 , CH3
aryl or vinyl ether
subs. arom. or fused
ring compounds
B
3,100-3,000
3,000-2,800
2,000-1,650
1,597, 1,596
1,376, 1,364
900-700
i
3,415
3,550-3,300
3,100-3,000
3,000-2,800
2,000-1,650
1,595, 1,495
900-700
S
M
W
M
M
S
M
W
M
W
W
W
S
CH, aromatic
CH, aliphatic
combination bands,
aromatic rings
C=C, aromatic
C-CH3
T(CH), several
aromatic rings
NH, secondary amine
OH, alcoholic
CH, aromatic
CH, aliphatic
combination bands
aromatic rings
C=C, aromatic
T(CH), several
aromatic rings
to
Ul
(continued)
-------
TABLE F-3 (continued)
r
LC3
LC4
C
3,030
2,960
1,925, 1,800
1,600
1,525
1,505
1,460, 1,440
1,430
1,380, 1,370
1,315, 1,300,^
1,265, 1,240,
1,200, 1,185,
1,165-1,135, >
1,110, 1,100,
1,040, 1,030,
1,000, 980-
928
885
860, 840
820, 780, 760-1
730, 715 /
3,335
3,030
2,960
1,695
1,600, 1,515
1,460, 1,450
S aromatics
W C-H stretch
W
M aromatic
W
M
Si C(CH3). C=C
MJ X
W C(CH3)3
W aromatics
M ) aromatics
Sf
S aromatics C-CSL
S OH or NH
M Aromatics
S C-H stretch
S aldehyde or ketone
M aromatics
S C(CH3)v
X
D
3,430 W OH, N-H
3,050 S aromatic Cll
2,920 W aliphatic CH
1,595, 1,480 W aromatic ring
1,465 S aliphatic
1,440 M aliphatic, alkenes
815, 775, 740 Si aromatic
840, 710 Mf substitution
1,265 weak peak
3,400 M -NH, -OH
3,060 M aromatic CH
2,960, 2,920 S aliphatic CH
2,850
2,220 M nitriles
1,700 S carbonyls
1,600 S broad, aromatic ring,
amines, amide,
carboxylic acid
Ni
ON
(continued)
-------
TABLE F-3 (continued)
LC4
C
1,380 M
1,335 M
1,265, 1,235 M
1,130, 1,075, W
970-925
845-800 M
780-720 S
C(CH3)2
C=C
C(CH3)3
aroroatics
D
1,480 W aromatic ring
1,450 S broad, alkanes
1,260 M aromatic ether,
phenols, carboxylic
acids, esters
1,130 M aliphatic ethers,
phthalates
1,080, 1,020 W aromatic overtones
800, 750 S aromatic substitution
1,325, 1,240, weak peaks
920
N>
(continued)
-------
TABLE F-3 (continued)
,C5
LC6
A
3,400
(broad)
3,050
2,850, 2,920
2,220
1,700
1,600
1,050
750
3,400
3,050
2,850, 2,920
1,710
1,680
1,600
1,450
1,060
740
W
W
W
W
M
M
VS
(broad)
M
M
(broad)
W
M
S
M
M
M
S
(broad)
M
OH, NH
unsaturated CH
saturated CH
-C=N
acid, ke tones
ring vibrations
Si-0-, ethers
subs. arom. , C-C£,
fused rings
OH, NH
unsaturated CH
saturated CH
acid, ketones
mono subs . amide ,
ketones
ring vibrations
CH2
Si-0-, ether
subs, pyridine, C-C8,
B
3,500-3,300
3,100-3,000
3,000-2,800
2,215
750
1,695, 1,595
1,450
3,600-2,200
3,100-3,000
3,000-2,800
1,709
1,600, 1,500
750-680
1,235
W
W
W
M
S
M
M
M
S
M
S-M
OH, alcoholic
CH, aromatic
CH, aliphatic
-CHN, nitrile
C-C£ or T(CH),
aromatic rings
minor absorption
maxima
OH, acidic
CH, aromatic
CH, aliphatic
C=0, acidic
C=C, aromatic
C-CS. or T(CH),
aromatic rings
minor absorption
maximum
N>
00
(continued)
-------
TABLE F-3 (continued)
LC5
.
LC6
C
3,335 M
3,030 M
2,960 S
1,725 S
1,680 M
1,625 M
1,600 S
1,540 W
1,450 S
1,305-1,280,1 W
1,250-1,190 /
1,135, 1,075 W
825, 815 W
740 S
700 M
3,450-3,335 W
3,030 W
2,960 M
1,725 S
1,665 W
1,600 S
1,460 8
OH or NH
aromatics
C-H stretch
C=0, esters
C=0, acids, ketone,
aldehyde
aromatics
C(CH3)
X
aldehyde, ketone,
nitro compounds,
arylamine
aromatics
N-H or 0-H
aromatic
C-H stretch
C=0, esters
C=0, aldehyde, ketones
aromatics
C(CH3)V
A
D
3,400 M -OH
2,960, 2,920 M aliphatic CH
2,850 W aliphatic CH
1,715 S carbonyls
1,600 W amides, amines,
aromatic ring
1,450 W aliphatics
1,260 W aromatic ethers,
aromatic alcohols,
esters
1,120 W aromatic overtones,
aliphatic ethers
840, 800, 740, W aromatic substitution
700
3,300 H Broad, -OH, -NH
2,960, 2,920, M aliphatic CH
2,850
1,710, l,725sh S carbonyls
1,600 M benzene ring, amines,
heterocyclic N
1,450 M aliphatics
740, 720, 700 M aromatic substitution,
amines
l,275br weak peak
10
VO
(continued)
-------
TABLE F-3 (continued)
LC6 1,335 M
1,305 S
1,280 S
1,250-1,110) W
770-740
aldehyde
aldehyde, ketone,
phenyl amines
aromatics
(continued)
-------
TABLE F-3 (continued)
LC7
LC8
A
3,400 S(br)
2,920 W
1,620 M
OH, NH
saturated CH
C=C
.Spectrum similar to blank #7.
3,400 S(br)
1,630 M
1,400 M
OH, NH
C=C
Spectrum similar to blank //7.
B
3,600-3,200
3,100-3,000
3,000-2,800
1,710
1,600, 1,500
800-700
1,280
M
M
S
S
M
M
OH, acidic
CH, aromatic
CH, aliphatic
C=0, aliphatic
C=C, aromatic
T(CH), aromatic rings
minor absorption
maximum
Not reported
(continued)
-------
TABLE F-3 (continued)
c
LC7 4,000
2,960
1,640
1,410
1,250
1,110
1,085-1,065
770-715
LC 8 3,335
3,225
3,075
2,960
1,725
1,650-1,560
1,470-1,380
1,290-1,250
1,190, 1,125,
1,085, 870,
770-750, 715-
690
S H20
M C-H stretch
S H20
M
M C-0 stretch
M)
M > Aroma tics
w)
W OH or NH
W N-H or OH
W aromatics
W C-H stretch
W C=0
W aromatics
W C(CH3)3
W C-0 stretch
W aromatics
D
No IR bands
3,400 S -OH, -NH
(broad)
1,630 W carboxylates
-------
APPENDIX G
LRMS RESULTS:
CATEGORIES IDENTIFIED IN
PHASE II SAMPLES
133
-------
TABLE G-l. LRMS RESULTS: CATEGORIES IDENTIFIED IN ARTIFICIAL SAMPLE IN CH2CL2, ALIQUOT 1
LCI
LC2
, LC3
>
te
LC4
Categories
Aliphatic hydrocarbons
Aliphatic hydrocarbons
Halogenated aromatic hydrocarbons
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic sulfur compounds
Esters, phthalates
Aromatic hydrocarbons
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic sulfur compounds
Aromatic hydrocarbons
Nitro aromatic hydrocarbons
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Esters
Cat boxy lie acids and derivatives
Lab A
100
10
100
100
10
100
100
100
100
100
100
100
100
100
10
Lab B
100
100
100
100
100
10
100
100
10
Lab C
NR
NR
NR
NR
Lab D
NR
10
100
Trace
NR
NR
(continued)
-------
TABLE G-l (continued)
LC5
LC6
LC7
Categories
Aromatic hydrocarbons
Nitro aromatic hydrocarbons
Fused alternate, nonalternate HC's
MW <216
MW >216
Esters
Carboxylic acids and derivatives
Aromatic hydrocarbons (substituted)
Nitro aromatic hydrocarbons
Ethers
Phenols
Esters
Heterocyclic nitrogen compounds
Sulfonic acids, sulf oxides
Carboxylic acids and derivatives
Ethers
Phenols
Heterocyclic nitrogen compounds
Sulfonic acids, sulf oxides
Carboxylic acids and derivatives
Lab A
100
1
1
1
10
10
100
100
100
100
1
10
1
1
1
Lab B
100
10
10
10
100
10
100
100
Lab C
NR
10
100
10
NR
Lab D
NR
10
100
NR
Cn
(continued)
-------
TABLE G-l (continued)
LC8
Categories
Ethers
Phenols
Esters
Heterocyclic nitrogen compounds
Carboxylic acids
Inorganics
Lab A
10
10
1
1
1
1
Lab B
100
Lab C
NR
Lab D
NR
o\
-------
TABLE G-2. LRMS RESULTS: CATEGORIES IDENTIFIED IN ARTIFICIAL SAMPLE ON FLYASH MATRIX, ALIQUOT 1
u
LCI
LC2
LC3
LC4
Categories
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Halogenated aromatic hydrocarbons
Sulfur
Aromatic hydrocarbons
Halogenated aromatic hydrocarbons
Fused alternate, nonalternate HC's
Aromatic hydrocarbons
Benzenes, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic nitrogen compounds
Sulfur
Aromatic hydrocarbons
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
Ke tones
Heterocyclic oxygen compounds
Heterocyclic nitrogen compounds
Lab A
100
10
1
100
100
100
100
10
1
10
10
100
Lab B
100
100
100
100
100
100
100
100
100
100
Lab C
NR
NR
NR
NR
Lab D
100
1
100
100
10
10
10
100
10
10
(continued)
-------
TABLE G-2 (continued)
LC4
(cont'd)
LC5
LC6
Categories
Heterocyclic sulfur compounds
Esters
Sulfur
Unclassified
Aromatic hydrocarbons
Fused alternate, nonalternate HC's
MW <216
Phenols
Amines
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Esters
Carboxylic acids and derivatives
Halogenated aromatic hydrocarbons
Fused alternate, nonalternate HC's
MW 216
Alcohols
Phenols
Nitrophenols
Amines
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Amides
Carboxylic acids and derivatives
Lab A
10
100
1
100
10
10
100
1
10
1
100
100
10
100
Lab B
100
100
100
100
100
100
100
100
Lab C
NR
NR
Lab D
10
10
100
10
100
100
100
100
10
10
u>
oo
(continued)
-------
TABLE G-2 (continued)
1 1
vc
LC7
LC8
Categories
Fused alternate, nonalternate HC's
MW <216
Alcohols
Phenols
Nitrophenols
Esters
Amines
Heterocyclic nitrogen compounds
Amides
Carboxylic acids and derivatives
Phenols
Esters
Heterocyclic nitrogen compounds
Carboxylic acids and derivatives
Inorganics
Lab A
_ _
10 .
10
10
10
10
10
1
1
1
10
Lab B
100
100
100
100
100
100
Lab C
NR
NR
Lab D
100
100
-------
TABLE G-3. LRMS RESULTS: CATEGORIES IDENTIFIED IN FIELD SAMPLE, XAD-2 EXTRACT, RUN 1
LC 1
LC 2
LC3
LC4
Categories
Aliphatic hydrocarbons
Sulfur
Aliphatic hydrocarbons
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Es ter s , phthala tes
Heterocyclic nitrogen compounds
Heterocyclic sulfur compounds
Aliphatic hydrocarbons
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic sulfur compounds
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Heterocyclic nitrogen compounds
Lab A
1
100
100
10
10
100
100
10
10
10
100
Lab B
100
100
100
10
10
100
100
100
100
100
100
10
Lab C
NR
10
100
10
100
NR
Lab D
NR
1
100
1
100
NR
(continued)
-------
TABLE G-3 (continued)
LC5
LC6
LC7
Categories
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Ke tones
Nitriles
Heterocyclic nitrogen compounds
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
Ketones
Nitriles
Phenols
Esters, phthalates
Heterocyclic nitrogen compounds
Carboxylic acids
Benzenes, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
Ketones
Nitriles
Esters
Heterocyclic nitrogen compounds
Carboxylic acids
Lab A
10
100
100
100
>
10
10
100
10
1
10
100
10
Lab B
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Lab C
NR
NR
NR
Lab D
NR
10
1
100
NR
(continued)
-------
TABLE G-3 (continued)
LC8
Categories
Benzene, substituted benzenes
Fused alternate, nonalternate HC's
MW <216
MW >216
Ethers
Phenols
Esters
Heterocyclic nitrogen compounds
Car boxy lie acids
Iron
Lab A
1
10
1
1
1
Lab B
100
100
100
10
Lab C
NR
Lab D
100
10
-------
APPENDIX H
ADDITIONAL ANALYTICAL RESULTS
FROM LAB C
1. TOTAL SAMPLE INFRARED SPECTRA
2. LRMS DATA
143
-------
TABLE H-l. RESULTS OF INFRARED SPECTROMETRIC ANALYSIS
Sample
identification
Artificial
sample in
methylene
chloride,
aliquot 1
Band
location,
cm"1
3040
2920,2850
1730
1610
1540
1500
1470
1350
1280
1270
1240,1220,
1175,1160
1090
1070
1045
1020
950,930,
920,870,
865,860,
790
820
810
760,750,
740
710
Band
intensity
W
S
S
W
S
W
M
S
M
S
W.
s ]
S
S
S
W ^
S
S
M
W >
*
Band
identification
C-H stretch aromatic
C-H stretch aliphatic
C=0 (esters)
Benzene ring
N0£ antisym stretch
Benzene ring
CH2
N02 sym stretch
OO-C stretch
C-O-C stretch (poss. Si-CH3)
Unassigned
Prob. benzene ring
substitution overlaying
Si-O-Si or Si-O-C
Benzene ring substitution
(poss Si-CH3 at 790)
(.continued)
144
-------
TABLE H-l (continued)
Sample
identification
Artificial
sample on
flyash
matrix,
aliquot 1
Band
location,
cm"1
3420
3060,3020
2920,2860
1950,1880,
1810
1730
1690
1605
1500
1460
1370
1350
1300-1150
1070
1035
970
950
920
850
820
760
700
Band
intensity
W
W
S
W
W
W
S
S
S
M
W
W "^
W
M
W
W
W
W
W
S
S
Band
identification
OH or NH
C-H stretch aromatic
C-H stretch aliphatic
Benzene ring overtones
C=0 (esters)
C=0 (aldehydes/ketones or
carboxylic acids)
Benzene ring
Benzene ring
CH2
CH3
CH3
Benzene ring overtones
(continued)
145
-------
TABLE H-l (continued)
Sample
identification
Field sample,
XAD-2 extract,
run 1
Band
location,
cm"1
3420
3050
2940,2920
2860
2400,2300
' 1930
1720
1670
1605
1510
1500
1490
1460
1445
1430
1370,1360
1305
1270
1250
1190
1140
1100
1040
1020
950
880
870
850
820
775
740
720
Band
intensity
W
S
S
W
W
W
W
W
S 1
W
M
w"
S
S
W
W
W
M
M
S
M
W >
M
W
W
W
W
S
S
S
S
S ^
*
Band
identification
C=0 overtone
C-H stretch aromatic
C-H stretch aliphatic
Carboxylic acid
Benzene ring
C=0 (esters)
C=0 (aldehydes/ketones)
Benzene ring
CH2
CH2
Carboxylic acid
CH3
S=0 antisym stretch
C-O-C stretch
C-O-C stretch
C-O-C stretch
8=0 sym stretch
C-0 stretch
Benzene ring substitution
146
-------
TABLE H-2. ADDITIONAL LRMS RESULTS FROM LAB B AFTER RECALCULATION
Artificial sample in methylene chloride, aliquot 1, LC 3
1. Categories present
100 Fused ring hydrocarbons
10 Aromatic hydrocarbons
2. Subcategories, specific compounds
100 Chrysene (or isomer)
10 Aromatic hydrocarbons
1 Pyrene (or isomer)
3. Other
10 MW = 234 (probably fused ring aromatic)
10 M/e = 279
Artificial sample in methylene chloride, aliquot 1, LC 6
1. Categories present
10 Esters
10 Fused ring hydrocarbons
2. Subcategories, specific compounds
10 Phthalate esters
10 Chrysene (or isomer)
3. Other
1 m/e = 167
XAD-2 extract, run 1, LC 6
1. Categories present
10 Esters
2. Subcategories, specific compounds
10 Phthalate esters
3. Other
147
-------
APPENDIX I
LRMS RESULTS:
SPECIFIC COMPOUNDS IDENTIFIED
IN PHASE II SAMPLES
148
-------
TABLE 1-1. LRMS RESULTS: SPECIFIC COMPOUNDS IDENTIFIED IN ARTIFICIAL SAMPLE IN CH.CL-, ALIQUOT 1
22
LCI
LC2
LC3
a
>
S
LC4
m/e Specific Compound
422 aliphatic hydrocarbon, possibly
squalane
112 chlorobenzene
154 acenaphthene/biphenyl
184 dibenzthiophene
228 chrysene/benzanthracenes
234 naphthothianaphthene
278 dibenzanthracene
422 aliphatic hydrocarbon, possibly
squalane
154 acenaphthene/biphenyl
167 unidentified
184 dibenzthiophene
198 methyldibenzthiophene
202 pyrene/fluoranthene
212 dimethyl/ethyldibenzthiophene
226 benz[ghi]fluoranthene
228 chrysene/benzanthracenes
234 naphtholthianaphthene
279 unidentified
152 aminonitrotoluene
182 dinitrotoluene
184 dibenzthiophene
202 pyrene/fluoranthene
217 benzocarbazole
222 diethylphthalate
226 benzfluoranthene
228 chrysene/benzanthracenes
234 naphtholthianaphthene
298 me thy Is tea rate
Lab A
100
100
100
100
10
10
10
100
100
1
r
100
10
10
100
100
100
10
100
10
Lab B Lab C
100 NR
KTR
Wl\
100
100 NR
100(u)
100
100
100
10(u)
VTO
ni\
10
100(u)
100
100
100
10(u)
10
Lab D
NR
P (u)
100
Trace
NR
NR
(continued)
-------
TABLE 1-1 (continued)
LC5
LC6
«t
f\
d
LC7
m/e Specific Compound
152 aminonitrotoluene
182 dinitrotoluene
202 pyrene/fluoranthene
228 chrysene/benzanthracenes
270 methylpalmitate
298 nonadecanoic acid
298 methylstearate
94 phenol
108 cresol
129 quinoline
182 dinitrotoluene
214 dimethoxybiphenyl
222 diethylphthalate
230 ditolylsulfoxide
256 palmitic acid
270 methylpalmitate
284 stearic acid
316 unidentified
355 unidentified
370 unidentified
129 quinoline
186 biphenol/phenoxy phenol
214 dimethoxybiphenyl
230 ditolylsulfoxide
256 palmitic acid
262 unidentified
284 stearic acid
Lab A
1
100
1
1
1
100
10
100
10
100
100
100
10
10
Ku)
Ku)
Ku)
1
10
1
1
1
Ku)
Lab B
100
10
10
10
10
100
100 (u)
10
100 (u)
100
100
100(u)
100(u)
100
100
'Lab C
NR
(phthalate
esters;
aromatic
substituted
compounds)
NR
Lab D
NR
(aliphatic
carboxylic
acid, Ciy-
C18; dime-
thoxybenzoic
acid)
NR
(continued)
-------
TABLE 1-1 (continued)
LC8
m/e Specific Compound
129 quinoline
134 zinc chloride
182 unidentified
186 biphenol/phenoxyphenol
214 methoxyblphenyl
230 unidentified
256 palmitic acid
270 methylpalmitate
298 nonadecanoic acid
298 methylstearate
phthalate, not specifically identified
Lab A
1
1
10
10
1
1
1
1
Lab B
10(u)
10 (u)
10 (u)
100
~~
Lab C
NR
Lab D
NR
en
P present but not quantified.
u = peak at indicated m/e unidentified.
-------
TABLE 1-2. LRMS RESULTS: SPECIFIC COMPOUNDS IDENTIFIED IN ARTIFICIAL SAMPLE ON FLYASH MATRIX, ALIQUOT 1
LCI
i
>
LC2
m/e Specific Compound
77, 91, 105 benzene, alkyl series
128-156 naphthalene, alkyl series
240-560 alkanes
256 sulfur
258 hexachlorobutadiene
282 hexachlorobenzene
332 hexachloronaphthalene
>300 unidentified chlorinated
compounds
400 octachloropentafulvalene
Alkene and cyclic alkene
and diene
Alkyne and cycloalkene,
terpenes
106-148 alkylbenzenes
119 benzotriazole
178-206 phenanthrene/anthracene,
alkyl series
180-208 stilbene, alkyl series
192, 206,i naphthalene, naphtheno-
220, 236 substituted
220-330 alkylated aromatic hydro-
carbons
200-400 alkylated aromatic hydro-
carbons
284, 286 hexachlorobenzene
290-400 chlorinated material
400 octachloropentafulvalene
>400 polyhalogenated compounds
Lab A
100
1
10
1
1
100
100
10
1
-
Lab B
100
100
~~
10
100
100
10
Lab C
NR
NR
Lab D
1
1
100
10
100
100
p
10
10
100
p
to
(continued)
-------
TABLE 1-2 (continued)
LC3
m/e Specific Compound
92, 106, 122 benzene, alkyl series
104, 208 styrene and styrene dimer
117 indole
118 methylstyrene
128 naphthalene/azulene
129 quinoline
130 divinylbenzene
142 methylnaphthalene
152 acenaphthylene/biphenylene
155 phenylpyridine
167 carbazole
178 phenanthrene/anthracene
180 stilbene
181 styrylpyridine/methyl carbazole
180, 206, 208 partially saturated aromatics
180, 192, 194, alkyl substituted aromatic
206, 208 series
182 dimethylbiphenyl
192 methylanthracene/phenanthrene
192 sulfur
193 methyl acridine
193 methylbenzoquinoline,
naphthaquinaldine , or
phenylindole
194 methyl stilbene
194 phenylbenzimidazole
202 fluoranthene/pyrene
204 dibenzoheptafulvalene
206 diphenylbutadiene
207 methylphenylindole
208 diphenylbutene
210 benzil/ditolylethane/alkyl
carbazole
217 benzocarbazole
226 benzfluoranthene
Lab A
100
100
1
1
10
1
100
100
10
100
1
10
100
10
^^
Lab B
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Lab C
NR
Lab D
100
10
10
P(u)
P(u)
P(u)
"
in
U>
(con M
-------
TABLE 1-2 (continued)
LC3
(cont'd)
LC4
t
1
s
m/e Specific Compound
232 unidentified sulfur con-
taining material
234 hexahydrobenzanthracene
236 unidentified
200-400 alkylated polycyclic material
309 unidentified
>400 polyhalogenated material
180 (452) phenazine or phenanthroline
(halogenated)
104, 208 styrene/styrene dimer
117, 193, 207 indole and aryl and alkyl
substituted indole
129, 193 quinoline and aryl and alkyl
substituted quinolines
136 methyl benzoate
152 acenaphthylene/biphenylene
167, 181, 210 carbazole and alkyl
substituted carbazoles
178 phenanthrene/anthracene
179 acridine
180 stilbene
180, 192, partially substituted
194, 206, 208 aromatics; alkyl substi-
tuted aromatic series
180 (452) phenazine/phenanthroline
(halogenated)
182 dimethylbiphenyl
192 sulfur
193 methylacridine
Lab A
1
100
1
--
10
100
100
'
10
10
10
10
1
10
Lab B
100 (u)
100(u)
10
100
100
100
100
100
100
100
100
100
100
Lab C
NR
Lab D
P(u)
- -
None
Identified
(continued)
-------
TABLE 1-2 (continued)
LC4
(cont'd)
LC5
ro/e Specific Compound
194 methylstilbene
194 phenylbenzimidazole
195 dimethylcarbazole
200 phenothioxine
202 fluoranthene/pyrene
204 dibenzoheptofulvaline
206 diphenylbutadiene
208 diphenylbutene
242, 270 unidentified
119, 240 unidentified
200-400 polycyclics
232 probable sulfur species
84 thiophene/methylene chloride
94 phenol
104, 208 styrene/styrene dimer
117 indole
121 benzamide
121 aniline
129, 193 quinoline and aryl and alkyl
substituted quinoline
135 toluatnide
136 methylbenzoate
155 unidentified
178 anthracene/phenanthrene
180 stilbene
181 methyl carbazole
182 unidentified
193 phenyl indole
193 naphthoquinaldine
Lab A
10
10
10
100(u)
100(u)
100 (u)
1
1
10
100
1
10
1
1
10
Lab B
100
100
100
100
100
100
100
100
100
100
100
100 (u)
100
100
Lab C
NR
Lab D
P
10
100
10
P(u)
Ul
en
(continued)
-------
TABLE 1-2 (continued)
LC5
(cont'd)
, LC6
n
N
m/e Specific Compounds
194 methylstilbene
207 substituted indole
217 benzocarbazole
225 dibenzamide
236 diphenylthiophene
246 diphenylphenol
130, 240, 242 unidentified
>400 polyhalogenated compounds
Hydrazines
Long chain unsaturated acid
or ester
93 aniline
94 phenol
108 cresol
118 methyls tyrene
121 benzamide
129 quinoline
130 methylindene
135 toluamide
139 nitrophenol
178 anthracene/phenanthrene
181 methylcarbazole
182 unidentified
193 phenylindole/naphthaquinaldine
199 phenathiazine
207 methylphenylindole
213 unidentified
248 C13 species
282 hexachlorobenzene
Sulfate decomposition, S00 ,
SO + 2
3
Lab A
1
10
1
10
Ku)
100
100
10
10
100
10
10
10
10
1
1
1
Lab B
100
100
10
10
10
100
100
100
100
100
100
100
100(u)
100
100
100
100 (u)
Lab C
NR
Lab D
100
100
None
Identified
(continued)
-------
TABLE 1-2 (continued)
LC7
LC8
P = present
m/e Specific Compounds
93 aniline
104 unidentified
121 benzamide
130 methylindene
135 toluamide
139 nitrophenol
178 anthracene/phenanthrene
181 methylcarbazole
182 unidentified
193 methylbenzoquinoline,
naphthoquinaldine, or
phenylindole
199 phenothiazine
207 methylphenylindole
213 unidentified
223 unidentified
237 unidentified
240 unidentified
263 unidentified
281 unidentified
Phthalate, not identifiable
44 carbon dioxide
104 unidentified
121 benzamide
129 quinoline
134 zinc chloride
135 toluamide
163 unidentified
181 methylcarbazole
182 unidentified
186 biphenol/phenoxyphenol
193 aryl substituted quinoline
199 phenothiazine
207 methylphenylindole
phthalate, not identifiable
Lab A
10
10
10
10(u)
10
10
10(u)
10 (u)
10(u)
10(u)
Tr^__
10
10
1
10
1
10
1
Lab B
10(u)
100
10
100
100
100
100
100(u)
100
100
100
100 (u)
100 (u)
_
10(u)
10
100
100
100
100(u)
100
100
100
^" "~
Lab C
MR
NR
Lab D
F(u)
P(u)
None
Identifie
but not quantified.
u peaU at indicated m/e unidentified.
Cn
-------
TABLE 1-3. LRMS RESULTS: SPECIFIC COMPOUNDS IDENTIFIED IN FIELD SAMPLE, XAD-2 EXTRACT, RUN 1
LCI
LC2
»
LC3
Specific Compounds
240-380 alkanes
256 sulfur
128-170 azulene/naphthalenes
142 methylnaphthalene
152 acenaphthylene/biphenylene
153 unidentified
154 biphenyl/acenaphthene
167 carbazole
178 anthracene/phenanthrene
184 dibenzthiophene
192 methylanthracene/phenanthrene
202 pyrene
216 benzof luorene/methylpyrene
230 terphenyl
182, 196, 220 unidentified PAH
228-242 chrysene (isomers)
242-268 benzo(a)pyrene (isomers)
278 benzochrysene
200-300 unidentified polycyclics
Ester, phthalate
Benzanthracene
Hydrocarbons
128-170 naphthalene/alkyl naphthalene
152 acenaphthylene/biphenylene
154 acenaphthene/biphenyl
166 methylacenaphthylene
168 methylbiphenyl
178 anthracene/phenanthrene
Lab A
1
100
10
10
10
100
10
100
100
10
10
Ku)
100
100
10
100
Lab B
100
10
10
100
100(u)
100
10
100
100
100
10
10
100
100
100
100
Lab C
NR
100
100
10
Lab D
NR
100
100
100
100
100
100
10
1
1
10
Ln
00
(continued)
-------
TABLE 1-3 (continued)
LC3
(cont'd)
LC4
Specific Compounds
184 dibenzthiophene
192 methylanthracene/phenanthrene
202 pyrene/fluoranthene
216 benzofluorene/methylpyrene
218 benzylnaphthylene
226 benzfluoranthene
228 chrysene/benzanthracenes
252 benzpyrenes, etc.
276 benzoperylene, etc.
278 dibenzanthracenea, etc.
302 dibenzpyrene, etc.
200-300 unidentified PAH
343, 357, 371 unidentified
167 carbazole
178 anthracene/phenanthrene
180 phenazine/phenanthroline
181 methyl carbazole
195 dimethyl carbazole
202 pyrene/fluoranthene
216 benzofluorene/methylpyrene
217 benzocarbazole
226 benzfluoranthene
228 chrysene, triphenylene, etc.
252 perylene, benzpyrene,
ben z f 1 uor an thene
267 dibenzocarbazole
276 benzoperylene, etc.
278 picene/benzchrysene
200-280 unidentified polycyclics
200-400 unidentified polycyclics
Lab A
10
100
100
10
100
10
10
10
10
10(u)
Ku)
100
10
10
10
10
10
10
10
10
10
10
1
Lab B
100
100
100
100
100
100
10
10
10
100
100
100
100
100
10
10
10
~
Lab C
___
100
100
100
10
10
NR
Lab D
100
100
10
10
NR
en
so.
(continued)
-------
TABLE 1-3 (continued)
LC5
LC6
Specific Compounds
152 acenaphthylene/biphenylene
153 naphthoisocyanid/3-naphtho-
nitrile
154 acenaphthene/biphenyl
167 carbazole
178 anthracene/phenanthrene
179 acridine
192 methylanthracene/phenanthrene
193 methylacridine
194 unidentified
202 pyrene/fluoranthene
203 cyanoanthracene
217 benzocarbazole
220 diphenylimidazole/
diphenylpyrazole
228 chrysene, triphenylene, etc.
230 benzanthrone
244 methylbenzanthrone
280 dibenzofluorenone
191, 234, 270 unidentified
200-400 unidentified
94 phenol
108 cresol
122 benzoic acids
152 acenaphthylene/biphenylene
153 beta-naphthonitrile
154 acenaphthene/biphenyl
167 carbazole
168 methylbiphenyl
179 acridine
Lab A
100
10
10
10
10
10(u)
10(u)
10
10 (u)
100
10
10
10(u)
Ku)
10
10
10
10
100
Lab B
100
100
100
10
100
100
100 (u)
100
100
100
100
100(u)
10(u)
100
100
100
100
100
~
Lab C
NR
NR
Lab D
NR
100
100
O\
o
(continued)
-------
TABLE 1-3 (continued)
LC6
(cont'd)
LC7
Specific Compounds
180 fluorenone, dihydroanthracene ,
dihydrophenanthrene
193 methylacr idine , phenylindole,
methylbenzoquinoline ,
6-naphthoquinaldine
194 methylfluorenone
202 pyrene/fluoranthene
203 azapyrene
204 unidentified
207, 208, 243
253 polycyclic components
220 diphenylimidazole/
diphenylpyrazole
229 anthraquinoline
230 benzanthrone/terphenyl
244 methylbenzanthrone
278 dibutylphthalate/dibenzo-
acridine
280 dibenzofluorenone
200-350 unidentified
122 benzoic acid
129 quinoline
143 methylquinoline
152 acenaphthylene/biphenylene
153 beta-naphthonitrile
154 acenaphthene/biphenyl
167 carbazole
178 phenanthrene/anthracene
179 acridine
192 methylphenanthrene/anthracene
Lab A
100
10
10
10 (u)
10(u)
10 (u)
10
10
10
10
10
Ku)
10
100
100
1
100
Lab B
100
100
100
100 (u)
100
100
10 (u)
10
100
100
100
100
100
10
100
Lab C
NR
Lab D
100
10
100
NR
(continued)
-------
TABLE 1-3 (continued)
LC7
(cont'd)
LC8
Specific Compounds
193 methylacridine/phenylindole/
beta-naphthoquinaldine
202 pyrene/fluoranthene
203 cyano-anthracene
217 benzocarbazole
229 anthraquinoline
230 benzanthrone/terphenyl
390 dioctylphthalate
122 benzoic acid
126 FeCl2
129 quinoline
157 dimethylqulnoline
178 phenanthrene/anthracene
186 biphenol/phenoxyphenol
202 pyrene/fluoranthene
214 dimethoxybiphenyl
228 chrysenes, etc.
278 unsaturated carboxylic acid
322 Fe2Cl6
390 dioctylphthalate
Lab A
10
100
1
1
1
10
1
1
1
10
1
1
1
Lab B
100
100
100
100
10
100
100
100
10
'"
Lab C
NR
NR
Lab D
NR
P
~~
u = peak at indicated m/e unidentified.
P = present but not quantified.
-------
. TECHNICAL REPORT DATA
(fieaje read Inuntctiom on the reverse before completing)
1. REPORT NO.
EPA-600/7-79-032
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Level 1 Environmental Assessment Performance
Evaluation
5. REPORT DATE
February 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Eva D. Estes
Franklin Smith, and Denny E. Wagoner
B. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
INE624
11. CONTRACT/GRANT NO.
68-02-2612. Task 21
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final: 6/77 - 10/78
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES
541-2557.
project officer is William B. Kuykendal, MD-62, 919/
is. ABSTRACT T^e report gjves results of a two-phased evaluation of Level 1 environ-
mental assessment procedures. Results from Phase I, a field evaluation of the
Source Assessment Sampling System (SASS), showed that the SASS train performed
well within the desired factor of 3 Level 1 accuracy limit. Three sample runs were
made with two SASS trains sampling simultaneously and from approximately the same
sampling point in a horizontal duct. A Method-5 train was used to estimate the 'true'
particulate loading. The sampling systems were upstream of the control devices to
ensure collection of sufficient material for comparison of total particulate, particle
size distribution, organic classes, and trace elements. Phase n consisted of pro-
viding each of three organizations with three types of control samples to challenge
the spectrum of Level 1 analytical procedures: an artificial sample in methylene
chloride, an artificial sample on a flyash matrix, and a real sample composed of
the combined XAD-2 resin extracts from all Phase I runs. Phase H results showed
that when the Level 1 analytical procedures are carefully applied, data of acceptable
accuracy is obtained. Estimates of intralaboratory and interlaboratory precision
are made.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Sampling
Analyzing
Dust
Trace Elements
Chemical Analysis
Organic Compounds
Particle Size
Pollution Control
Stationary Sources
Environmental Assess
ment
SASS Train
Particulate
13B
14B
07D
07C
11G
06A,06P
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
173
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
163
------- |