Environmental Monitoring Series
METHODS FOR DETERMINING THE
POLYCHLORINATED BIPHENYL
EMISSIONS FROM INCINERATION
AND CAPACITOR AND
TRANSFORMER FILLING PLANTS
Environmental Monitoring arid Support Laboratory
Offlco of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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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 ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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METHODS FOR DETERMINING THE TOTAL POLYCHLORINATED
BIPHENYL EMISSIONS FROM INCINERATION
AND CAPACITOR- AND TRANSFORMER-
FILLING PLANTS
By
Clarence L. Haile
and
Emile Baladi
EPA Contract No. 68-02-1780, Task 2
EPA Task Officer
W. J. Mitchell
Qua1ity As surance Branch
Environmental Monitoring and Support Laboratory
Research Triangle Park
North Carolina 27711
For
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park
North Carolina 27711
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DISCLAIMER
This report has been reviewed by the Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily re-
flect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
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FOREWORD
Midwest Research Institute under Task 2 of EPA Contract No.
68-02-1780 has developed sampling and analysis methods for PCB emissions
from industrial, sewage sludge, and municipal refuse incinerators and from
capacitor- and transformer-filling plants. The development and evaluation
of these methods are described in this report.
Approved for:
MIDWEST RESEARCH INSTITUTE
J. Shannon, Director
\1 Environmental and Materials
Sciences Division
August 23, 1977
ii
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PREFACE
In April 1976, the Quality Assurance Branch of EMSL, FTP, NC, was
directed to develop and validate a method for measuring the PCB emissions
from incinerators and from capacitor- and transformer-filling plants. From
an extensive review of the available literature and from consideration of
the various stack conditions that would be encountered, a tentative method
was proposed and submitted to Midwest Research Institute for evaluation.
The tentative method involved collecting the PCB's on a filter followed by
a solid adsorbent and analyzing for PCB's by converting all PCB's collected
to the decachlorobiphenyl (DCB; isomer.
Solid adsorbents were favored over the use of polyurethane foam
for the following reasons: (1) low background; (2) simple cleanup proce-
dure; (3) good quality control during manufacturing in relation to particle
size, purity, density, etc., and (4) ready availability. The chromatographic
grade adsorbent was preferred over the organic liquid for the following rea-
sons: (1) no evaporation during sampling; (2) much less chance for contam-
ination because the collector could be assembled in the laboratory, sealed,
shipped to the site, placed in the sampling train removed at the completion
of sampling, sealed, and then returned to the laboratory for sample recovery;
(3) less hazardous to use than organic liquids; and (4) no loss of collec-
tion efficiency as water condensed in the impingers. The use of a filter was
later deleted from the procedure because field studies under this contract
and similar field studies done by others found negligible amounts of PCB's
on the filters.
Perchlorination to convert all samples to the decachlorobiphenyl
species was selected as the most effective means to accurately determine
the PCB emissions from incineration sources because: (1) the electron cap-
ture detector response increases as the degree of chlorination increases;
(2) only one standard is necessary for quantitation; (3) the "fingerprint"
technique of quantitation, which involves relating the concentration of
PCB to the nearest Aroclor, would not be applicable to incinerator-type
sources, because different isomers might be destructed at different rates
and because the refuse can contain many different polychlorinated biphenyls;
and (4) the toxicity of the individual isomers is unknown so the intent of
any regulation would likely be to minimize the total PCB emissions rather
than the emissions of individual isomers.
William J. Mitchell
EPA Task Officer for Task
No. 2
EPA Contract No. 68-02-1780
iii
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ABSTRACT
A method for the sampling and analysis of PCB emissions from in-
dustrial, sewage sludge, and municipal refuse incinerators was developed
from laboratory and field evaluations at nine incineration plants. The
sampling method was based on modification of the Method 5 train, by remov-
ing the heated filter and adding a Florisil adsorbent tube, and sample re-
covery and PCB assay procedures were adapted from methods widely utilized
for the analysis of PCB residues in environmental samples. The precision
of the method, determined from field sampling in duplicate, was 13%.
The method was adapted for the determination of PCB emissions
from capacitor- and transformer-filling plants. The sampling train was
adapted by removing the ice-cooled impingers. The method was evaluated
by sampling ambient air in impregnation rooms of two capacitor-filling
plants. PCB concentrations as high as 2,500 pg/m^ were determined with
PCB breakthrough of < 0.15% (determined from a second Florisil tube con-
nected in series). The PCB method is appended to this report.
This report is submitted in fulfillment of Task 2 of Contract No.
68-02-1780 by Midwest Research Institute under the sponsorship of the
Environmental Protection Agency.
IV
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TABLE OF CONTENTS
Page
Acknowledgments ix
1.0 Introduction 1
2.0 Development of the Preliminary PCB Method for Incinerators. 2
2.1 Development of a Preliminary Sampling System. . . 2
2.2 Development of the Analytical Protocol 12
3.0 Evaluation of the PCB Method for Incinerators 20
3.1 Laboratory Evaluation of Sampling Train
Efficiency 20
3.2 Field Evaluations 22
3.3 Confirmation of PCB Residues from Incinerators. . 35
4.0 Application of the PCB Method to Emissions from Capacitor-
and Transformer-Filling Plants 45
4.1 Method Adaptation 45
4.2 Field Evaluations 45
5.0 Conclusions 48
6.0 Literature Cited 49
Appendix - Draft Method, Determination of Total Polychlorinated
Biphenyl (PCB) Emissions from Stationary Sources .... 50
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LIST OF FIGURES
Figure Title Page
1 Laboratory Sampling Train for the Evaluation of
Adsorbents 3
2 Candidate PCB Sampling Trains.
3 Elution Patterns of Aroclor 1221, 1242, and 1254 on an
OV-210 Column Operated Isothermally at 160, 170 and
210°C, Respectively 13
4 Schematic Illustration of the Mission, Kansas, Sewage
Sludge Incinerator 23
5 Schematic Illustration of the Rollins, Inc., Industrial
Incinerator, Deer Park, Texas 25
6 Schematic Illustration of the Miami (FL) No. 1
Municipal Incinerator 28
7 Schematic Illustration of Bade Co. (FL) N.E. Municipal
Incinerator 29
8 Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 1 (South
Side) 30
9 Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 2 (Batch),
Inlet 31
10 Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 2 (Batch),
Outlet 32
H Broward Co. Plant No. 2, Pompano Beach, Florida,
Incinerator No. 4 33
12 SIM-GC/MS Chromatograms of m/e 290 and 292 for 2.0 ng
Aroclor 1254 36
13 SIM-GC/MS Chromatograms of m/3 324 and 326 for 2.0 ng
Aroclor 1254 37
14 SIM-GC/MS Chromatograms of m/3 360 and 362 for 2.0 ng
Aroclor 1254 38
vi
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LIST OF FIGURES (concluded)
Figure Title Page
15 SIM-GC/MS Chromatograms of m/e 290 and 292 for Sample 2A
from the Rollins Industrial Incinerator .......... 39
16 SIM-GC/MS Chromatograms of m/e 324 and 326 for Sample 2A
from the Rollins Industrial Incinerator 40
17 SIM-GC/MS Chromatograms of m/e 360 and 362 for Sample 2A
from the Rollins Industrial Incinerator 41
18 SIM-GC/MS Chromatograms of m/e 290 and 292 for Sample 2
from the Blue River Sewage Sludge Incinerator 42
!9 SIM-GC/MS Chromatograms of m/e 324 and 326 for Sample 2
from the Blue River Sewage Sludge Incinerator 43
20 SIM-GC/MS Chromatograms of m/e 360 and 362 for Sample 2
from the Blue River Sewage Sludge Incinerator 44
vii
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LIST OF TABLES
Table Title Page
1 Results of Adsorbent Evaluations at Low Sampling Rates . . 4
2 Results of Adsorption Evaluations at High Sampling Rates . 5
3 Results of Adsorption Evaluations at Elevated
Temperatures and Moisture in Sampled Gases 6
4 Results of Adsorption Evaluations at Different Run Times . 7
5 Results of PCB Train Evaluation Testing at Bade County
(Florida) Municipal Refuse Incinerator 11
6 Results of Extraction Recovery Studies 14
7 Yields of DCB from Selected Chlorobiphenyls by
Perchlorination Under Different Reaction Conditions. . . 18
8 Percent Yields of DCB from Chlorobiphenyls by
Perchlorination at 160°C for 2 Hr 18
9 Sampling Efficiency of PCB Sampling Train. ... 21
10 Distribution of Aroclor 1254 Spike in the Sampling Train . 21
11 Summary of PCB Results for Two Sewage Sludge Incinerators. 24
12 Summary of PCB Results for Two Industrial Incinerators . . 26
13 Summary of PCB Results for Five Municipal Refuse
Incinerators 34
14- Summary of PCB Results for Two Capacitor-Filling Plants. . 46
viii
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ACKNOWLEDGMENTS
Midwest Research Institute would like to thank the cities of
Miami, Florida; Kansas City, Missouri; and Mission, Kansas; Dade and
Broward Counties, Florida; and Rollins Environmental Services, Inc., for
their cooperation and assistance in sampling their incineration facilities
as a part of our field evaluations.
Technical assistance for the laboratory evaluations was provided
by Paul Cramer, Jon Onstot, Keith Charter, Sue Long, Joyce Wilkerson, and
Rene Van der Hayden. Assistance for field sampling was provided by Tom
Merrifield, Bill Maxwell, Jon Onstot, Bruce DaRos, and Chris Cole.
Dr. William J. Mitchell, the EPA task officer for this project,
is thanked for his guidance throughout the program and for his assistance
in securing permission for sampling at five municipal incineration plants.
ix
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1.0 INTRODUCTION
The release of polychlorinated biphenyls (PCBs) into the environ-
ment has caused considerable concern because of their chronic toxicities,
resistance to chemical and/or biochemical degradation, and their tendency
to bioaccumulate in food chains (including man). The chemical stability
and dielectric properties of PCBs have been utilized in a variety of appli-
cations. Prior to 1970, typical PCB uses were as plasticizers, heat trans-
fer agents, as components of cutting oils and other special lubricants, as
components of hydraulic fluids, in formulations of paints and other protec-
tive coatings, in adhesives, in carbonless reproducing paper, and as dielec-
tric fluids in electrical capacitors and transformers. Following the iden-
tification of PCB residues in a variety of ecosystems, the Monsanto Company,
sole producer of PCBs in the United States, restricted all PCB sales after
1972 to "closed system" uses, largely as dielectrics in capacitors and
transformers. However, some PCBs and PCB-containing materials are still
imported.
The diverse and considerable usage of PCBs during the middle of
this century complicates the disposal of wastes containing these hazardous
materials in a manner consistent with sound environmental management. Of
the 1.4 billion pounds of PCBs sold in the United States since 1929, about
750 million pounds were exported, and about 500 million pounds have already
entered the environment, mostly via landfills.—' The eventual disposal of
the PCB-containing materials currently in service will likely result in
their inclusion in industrial and municipal wastes. A part of these wastes
are processed by incineration in industrial incinerators, municipal refuse
incinerators, and sewage sludge incinerators.
Assessing the emission of PCB residues into the environment re-
quires, in part, an evaluation of PCB emissions from these waste disposal
facilities. This investigation was designed to develop appropriate sampling
and analysis methods for determining PCB emissions from industrial, munici-
pal refuse, and sewage sludge incinerators. A method was formulated so as
to provide a standard reference method for PCB emissions from these station-
ary sources. In addition, the method was adapted for the measurement of
emissions from capacitor- and transformer-filling plants, the current major
users of PCB materials in the United States. This report describes the de-
velopment and evaluation of the method. The method is appended to this re-
port.
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2.0 DEVELOPMENT OF THE PRELIMINARY PCB METHOD FOR INCINERATORS
2.1 Development of a Preliminary Sampling System
The design criteria for the development of the PCB sampling train
included efficient, isokinetic collection of both vaporous and particulate-
associated PCB residues (although not necessarily fractionated), from a
variety of incinerator stack emissions (e.g., cool to hot gases, dry to
supersaturated gases, etc.) in a form acceptable to the constraints of the
analytical protocol to be developed. In addition, the simplicity of con-
struction and operation and ruggedness under field sampling conditions were
considerations.
A number of devices have been used to extract PCBs and/or chlori-
nated pesticides from ambient air and stationary sources. Many of these were
reviewed by Margeson.—' The most promising of these include polyurethane
foam, the macroreticular resin Amberlite® XAD-2, Tenax®-GC, and Florisil.
The foam and resin have also been applied to the extraction of the same com-
pounds from waterso Although polyurethane foam has the attractive property
of causing very little resistance to flow, cleaning the foam prior to use in-
volves a lengthy series of extractions and blanks can be troublesome.
Although evaluated at low flows (2-3 liters/min) Florisil has been
shown to be a very effective PCB adsorbent.—' In addition, as silicate salt,
Florisil is normally activated by heating to temperatures that destroy most
organics so that very clean blanks may be achieved. XAD-2 has been utilized
for the collection of a variety of organic species from air, including flue
gases,—' In particular, Amberlite® XAD-2 is the adsorbent used in the EPA
Source Assessment Sampling System (SASS train). A stationary source sampling
f^M ^ /
train incorporating Tenax^-GC has been developed and tested.—' However, re-
ports of in situ decomposition of Tenax during sampling may'contribute to
blank problems.—'
2.1.1 Evaluation of adsorbents; Adsorbents selected for evalua-
tion, Florisil® (60/100 mesh PR grade, Floridin Company), XAD-2® (20/50 mesh,
Mallinckrodt, Inc.) and Tenax®-GC (35/60 mesh, Applied Sciences Laboratories,
Inc.) were cleaned by overnight Soxhlet extraction with hexane and then dried
overnight at 110°C. The Florisil was activated by heating to 650°C for 2 hr
in a muffle furnace. Adsorbents were stored at 110°C until immediately prior
to use.
Trapping efficiencies were determined by sampling laboratory air
spiked with PCBs utilizing the sampling configuration shown in Figure 1.
Small volumes (1-10 ul) of PCB standard solutions were deposited in the de ,
pression at the bottom of the sample introduction tube and were volatilized
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'Sample Introduction Tube
-Adsorbent
•Glass Wool
•Adsorbent Tube
Calibrated
Rotometer
|Figure 1 - Laboratory Sampling Train for the
Evaluation of Adsorbents
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into the airstream sampled by heating with a heat gun. Following sampling
the source tube was removed and thoroughly rinsed with hexane. The adsor-
bent tube was eluted with 50 ml hexane. Both source and adsorbent tube ex-
tracts were concentrated to 5.0 ml in Kuderna-Danish evaporators and assayed
by gas chromatography with electron capture detection (GC-EC) for the PCBs
spiked into the sampling stream. The chromatographic column, 1.8 m x 2 mm ID
glass packed with 3% OV-210 on 100/120 mesh Supelcoport®, was eluted with
30 ml/min of nitrogen. Injector and detector temperatures were 220 and 300°C,
respectively. The column temperature was held isothermally at 165 to 200°C,
depending on the particular PCB material assayed. Trapping efficiencies were
calculated from the weight of PCB in the adsorbent extract compared to the
weight spiked, corrected for the weight in the source tube extract.
For the preliminary trapping efficiency testing, the adsorbent
tubes were ^ 150 x 15 mm ID. The clean, dry adsorbent was weighed into the
tubes, tared with a plug of cleaned glass wool in the exit end, and a second
glass wool plug was added to contain the adsorbent. The volumes of adsorbents
placed in the tubes were very similar; however, the weights were quite differ-
ent because of density differences.
Test runs were completed with each of the three adsorbents with
each of three PCB compounds at sampling rates of about 3.5 liters/min. Sampled
air was spiked with 600 ng of 2,2'-dichlorobiphenyl (2CB), 600 ng of 2,4,2',5'-
tetrachlorobiphenyl (4CB), or 700 ng of 2,3,4,2',3',4'-hexachlorobiphenyl (6CB)
To get an indication of the restriction to flow caused by the adsorbent tubes,
the flow rate was set at 4.0 to 4.1 liters/min before the tubes were fitted to
the system. The 60/100 mesh Florisil provided the greatest restriction, reduc-
ing the flow rate by 31%; Tenax reduced the flow rate by 10%. The XAD-2 tube
caused only slight flow rate reduction, ^ 2%.
Tests were run for 10 min. The results of these tests are shown in
Table 1.
TABLE 1 .
RESULTS OF ADSORBENT EVALUATIONS AT LOW SAMPLING RATES
Recovery
2CB
4CB
6CB
adsorbent (g)
rate (liter/min)
°
Florisil
2.0 .
2.8
80.0
111
87.6
Adsorbent
Tenax
0.65.
3.7
78.4
107
103
XAD-2
1.2
4.0
69.3
92.2
83.3
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These results indicate that XAD-2 might be a less efficient PCB adsorbent.
A second series of tests was similarly completed at flow rates
near 20 liters/min and with larger (22 mm ID) tubes to better simulate the
sampling rates desired for isokinetic sampling. Flow restriction became a
serious problem in the Florisil tests, where a sampling rate of 17 liters/
min was the highest obtainable with the pumping system fitted to the train.
The results of these tests are shown in Table 2.
TABLE 2
RESULTS OF ADSORPTION EVALUATIONS AT HIGH SAMPLING RATES
f adsorbent (g)
; rate (liter/min)
Florisil
6.5
17
71.4
90.5
80.6
Adsorbent
Tenax
2.4
20
82.7
92.8
91.0
XAD-2
6.0
20
34.0
59.2
57.0
Recovery
2CB
4CB
6CB
Since the XAD-2 exhibited a much lower trapping efficiency for PCBs under
these conditions, no further testing was conducted with this material.*
Although the trapping efficiencies for Florisil and Tenax appeared
comparable and acceptable, the flow restriction of the Florisil could pose a
serious problem when high sampling rates are required. A sample of 30/60
mesh Florisil, Grade A, was received from Floridin Company for evaluation
to overcome the flow restriction problem. Since each batch of Florisil was
routinely activated at 650°C, similar to the activation process used by
Floridin Company to produce PR grade adsorbent, the activity of the treated
30/60 mesh A grade should be similar to that of the 60/100 mesh PR grade.
A third series of trapping efficiency studies with the 30/60 mesh Florisil
showed that the flow restriction was much less, similar to that experienced
with the 35/60 mesh Tenax. Recoveries of 74.3, 89.7, and 111% for 2CB, 4CB,
and 6CB, respectively, were found for 7.5 g of the coarser Florisil at a
sampling rate of 20 liters/min.
A specially prepared sample of XAD-2 was evaluted, however, as a part
of the selected PCB sampling train. See Section 3.1.
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In order to obtain information on the effects of higher gas stream
temperatures and moisture content, two recovery studies were conducted with
2CB and 6CB. In the first study, the adsorbent tube was enclosed in a heated
box held at 120°C. During the previous tests without the heated box, the ad-
sorbent temperature was near 50°C from heating of the sampled air with the
heat gun. In the second of these studies, two impingers were connected in
series to the inlet of the sample introduction tube. The first impinger con-
tained 100 ml of distilled water and the second was empty to trap entrained
water. The results of these tests are shown in Table 3.
TABLE 3
RESULTS OF ADSORPTION EVALUATIONS AT ELEVATED
TEMPERATURES AND MOISTURE IN SAMPLED GASES
120°C 120°C + High Moisture
Tenax Florisil Tenax Florisil
Weight of adsorbent (g) 1.5 5.0 1.5 5.0
Sampling rate (liter/min) 20 20 20 20
Recovery (%) . .
2CB I- 68.6 I- 58.6
6CB 53.4 49.9 44.3 50.9
a/ Severe interferences in the Tenax extract, 2CB, could not be
quantified.
From these limited experiments, the trapping efficiencies for both
adsorbents appear to be more affected by temperature of the adsorbent than
the moisture content of the gas stream. Hence, an efficient sampling train
design utilizing these adsorbents should allow for cooling of hot gases be-
fore introduction to the adsorbent.
In order to evaluate the trapping efficiencies of Florisil and
Tenax adsorbent traps at run times that might by typical of those required
in field sampling, a final series of recovery studies was conducted with run
times of 10 min, 2 hr, and 4 hr at ambient laboratory temperature and mois-
ture content. The results of these studies are shown in Table 4. Trapping
efficiencies were decreased by long run times, but not markedly so.
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TABLE 4
RESULTS OF ADSORPTION EVALUATIONS AT DIFFERENT RUN TIMES
Weight of adsorbent (g)
Sampling rate (liter/min)
Run Time:
10 min
2 hr
4 hr
10 min
4 hr
10 min
2 hr
4 hr
Florisil
7.5
20
59.4
47.9
47.0
99.7
82.2
96.9
91.2
Tenax
2.0
20
2CB Recovery (%)
62.4
40.
49.5
4CB Recovery (%)
85.9
79.4
76.2
74.1
73.9
a/ Assay of Tenax extract is suspect; interfering peaks in chromatograms.
Although their trapping efficiencies were not as good as desired for
the more volatile 2CB, Tenax and Florisil appeared to be roughly equivalent
as PCB adsorbents. Increasing the temperature of the adsorbents had a much
greater impact on their efficiencies than either the introduction of moderate
levels of moisture or long run times.
2.1.2 Design and preliminary evaluation of candidate PCB sampling
trains; Considering the PCB trapping evaluations of Florisil and Tenax, a
PCB sampling train utilizing these adsorbents must provide for cooling the
sampled gases (and likely condensation of water in saturated and supersatu-
rated gases and removal of entrained droplets) prior to passage of the gases
through the adsorbent trap. Several approaches to meeting these criteria
were evaluated. In most cases, ice-cooled impingers were employed to cool
and condense water from the sampled gases. One train design utilized a water-
cooled condenser for this purpose. Heated and/or unheated filters were
utilized to collect particulates or remove entrained water. The operating
characteristics of candidate train designs were evaluated under field condi-
tions by sampling at a sewage sludge incinerator of the Blue River municipal
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sewage treatment facility in Kansas City, Missouri. The goal of these tests
was to run at 20 liters/min for up to 4 hr. Since this evaluation was for
operability only, the contents of the trains were not assayed for PCB residues.
Several operating principles were apparent. In most cases, the com-
bination of one or more filters in series with the adsorbent tube generally
caused excessive resistance to flow and in many cases did not allow operation
at the desired flow rate. In addition, as particulates collected on filters,
flow restriction increased dramatically. Two train designs, diagrammatically
represented in Figure 2, exhibited acceptable operating characteristics.
In the case of Train A, a Graham condenser and flask were utilized to cool
the gases, condense and collect moisture. The condenser was modified with a
glass extension tube to hinder entrainment of condensed water into the gas
stream just in front of the adsorbent trap. A heated filter was placed in
front of the condenser to trap particulates and simplify cleanup of the con-
denser following sampling. In Train B a series of three ice-cooled impingers
similarly protect the adsorbent. Sampled gases were cooled and moisture con-
densed in the first two Greenburg-Smith impingers to which 100 ml of distilled
water were added. The third impinger, a modified Greenburg-Smith type,.was
included to trap entrained water. To protect the pumping system the adsorbent
tube was followed by two impingers. The first of these impingers held 100 ml
of a 10% sodium hydroxide solution to neutralize acidic gases, such as the
HC1 that is produced in the incineration of chlorinated hydrocarbons, and the
second had 300 g of silica gel to remove moisture.
The two train designs were further evaluated with both adsorbents
by field testing at the Dade County (NE) municipal refuse incinerator in
Miami, Florida. The same incinerator was also tested in evaluations described
in Section 3.2.3. Paired Trains A and B with either Florisil or Tenax adsor-
bents were operated simultaneously for each sampling run. Since only limited
testing was conducted, sufficient .sampling equipment was prepared in the lab-
oratory so that the trains could be disassembled and shipped back to the lab-
oratory for sample recovery and analysis. In this manner the results of the
evaluation were not biased by possible contamination during sample recovery
in the field and field operations were simplified.
Upon receipt of the trains at the laboratory, sample recovery was
initiated. The condensed water was batch extracted with three 100-ml por-
tions of hexane. The filters from Train A were extracted with three 50-ml
portions of hexane for 20 min each in a sonic bath. In order to determine
the extraction requirements for the adsorbents used for field sampling, each
trap was first eluted with 100 ml of hexane. The contents were then removed
and Soxhlet extracted for 4 hr with 170 ml hexane and the extracts assayed
separately. The requirements for rinsing the trains with organic solvents
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TRAIN (A
Probe
Heated
Area
Filter Holder
Warm Water Out-«-=
Chilled Water ln-»=
Modified Graham Condenser
Thermometer-
Adsorbent
Trap Tube
Check
Valve
/x
(i
\.
Metering
tern
lmpingerss.|ca
100ml 10% NaOH
Probe
TRAIN (T)
Adsorbent Tube
Thermometer
Check
Valve
•To Pump
and
Metering
System
Impingers \ rSilica Gel
\ J
100ml 10% NaOH
Figure 2 - Candidate PCB Sampling Trains
9
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were investigated by rinsing the trains with distilled water (which was then
extracted with hexane utilizing the same procedures as for condensed water)
and then with a small amount of acetone, to remove moisture from the glass,
prior to a thorough rinse with hexane. The extract of the aqueous rinses
and the combined acetone and hexane rinses for each train were assayed
separately.
All extracts were evaporated to ^ 5 ml, dried by passage through a
microcolumn (disposable pipette) of anhydrous sodium sulfate, and then cleaned
(*S\
up by shaking with 5 ml of concentrated sulfuric acid in vials with TFE -lined
screw caps. The PCB contents of the cleaned extracts were assayed by perchlo-
rination of the PCBs to decachlorobiphenyl (DCB) by procedures described in
Section 2.2 and then EC-GC analysis of the DCB. The chromatographic system
described in Section 2.1.1 was utilized with the column temperature main-
tained at 240°C.
Table 5 summarizes the results of these evaluations. Since the
sampling runs with the two adsorbents were conducted on different days, much
of the variability in the amount of PCB materials recovered may be related to
the variability of feed material and furnace conditions of the incinerator.
Hence, direct comparison of the two adsorbents was not possible. Also, com-
parisons of the results from Trains A and B for a particular run are not con-
clusive. Nonetheless, from these and the previous evaluations, Florisil was
selected as the best adsorbent alternative and Train B was selected as the
best train design. In the laboratory evaluations, Florisil exhibited trap-
ping efficiencies as good or better than those of Tenax. In addition, Flor-
isil extracts exhibited consistently negligible levels of interfering co-
extractants (likely resulting from the high activation temperature used on
this inorganic adsorbent), compared to frequently troublesome blanks exhibited
by Tenax extracts (as noted in Section 2.1.1). Although a minor consideration,
Florisil is much less expensive than Tenax.
The selection of Train B as the best alternative offered several
practical advantages. During the 4-hr test runs the pressure drop across
Train A was ^5.5 in. (140 mm) of Hg while the pressure drop across Train B
was only ^ 1 in. (25 mm) of Hg. In addition, the Train B design, essentially
a Method 5 train modified by the removal of the heated filter and the addi-
tion of the adsorbent tube, is simpler and more compact to handle in the
field and to maintain.
Examination of the PCB contents_recovered from the components of
the trains, Table 5, showed that simple elution of the adsorbent trap with
an extracting solvent (although sufficient to extract PCB residues follow-
ing laboratory evaluations) did not quantitatively extract PCB residues
collected in source samples. Hence, the more rigorous Soxhlet extraction
procedure must be used. In addition, rinsing of train components with hexane
10
-------
TABLE 5
RESULTS OF PCS TRAIN EVALUATION TESTING AT DADE COUNTY
(FLORIDA) MUNICIPAL REFUSE INCINERATOR
Adsorbent
Florisil (30/60 mesh)
Train—'
Date sampled
Run number
Sampling rate (liter/min)
Sampling time (hr)
Weight of adsorbent (g)
Total PCB content (yg)
Condensed moisture
Adsorbent (eluted)
Adsorbent (Soxhlet)
Filter
Probe rinse (water)
Probe rinse (hexane)
Train rinse (water)
Train rinse (hexane)
A
7/14/76
1
20
4
7.5
22.8
9.90
3.20
0.43
0.04
0.05
b/
12.70
B
7/14/76
1
20
4
7.5
10.4
4.55
10.2
,
0.31
2.00
2.90
6.10
Teriax (30/60 mesh)
A
7/15/76
2
20
4
2.0
0.72
6.25
0.73
0.80
0.10
0.07
0.16
1.30
B
7/15/76
2
20
4
2.0
3.25
3.80
0.22
-
0.06 .
6.902/
0.15
1.30
Total
49.1
36.5
9.4
15.7
a/ Shown in Figure 2.
b_/ This train was not rinsed with water.
cj Possibly due to contamination.
11
-------
is required to recovery PCB residues associated with the inner glass surface
of the train. The acetone prerinse is necessary to remove water from the
glass so that the water-immiscible hexane can effectively wet the surface.
2.2 Development of the Analytical Protocol
PCB residues have been assayed in a variety of environmental samples,
often by procedures designed to determine chlorinated pesticides as well. The
goal of the analytical development for PCB assays in stationary source emis-
sions, specifically from incinerators, was to adapt the procedures generally
employed for environmental samples and not to develop entirely new methods.
Modifications of these procedures were designed to take advantage of the
chemical stability of PCBs, by employing rigorous cleanup procedures inappro-
priate for pesticide/PGB assays, and to simplify quantification of "total"
PCB residues, as in the utilization of perchlorination methods. Hence, a
part of the analytical development described below involved verification
of PCB recoveries from the various analytical techniques employed. More ex-
tensive evaluation of cleanup procedures and optimization of quantitation
methods were also conducted.
2.2.1 Extraction procedures; Soxhlet extraction of PCB residues
from the solid adsorbent and three-fold batch extraction from aqueous samples
were employed for sample recovery. Quantitative recoveries were verified by
the extraction of samples spiked with Aroclor 1221 and 1254. Soxhlet extrac-
tors were assembled with 170 ml of hexane and a plug of clean glass wool
in the bottom of the sample holder, A 7.5 g portion of clean, activated Flor-
isil (30/60 mesh) was added to the sample holder. The adsorbent was spiked
with 10.5 tig Aroclor 1254 or 14.5 y.g of Aroclor 1221 by injecting concen-
trated solutions (1.0 lig/jil) below the surface of the Florisil. Following
extraction for 4 hr, the extracts were concentrated to 10.0 ml and assayed
by EC-GC. The chromatographic system described in Section 2.1.1 was utilized
with the column temperature held at 160°C for Aroclor 1221 assays and 210°C
for Aroclor 1254 assays. Distilled water (200 ml) samples were similarly
spiked in 1,000 ml separatory funnels. The spiked waters were batch extracted
with three 100-ml portions of hexane, the combined extracts concentrated
to 10.0 ml (Kuderna-Danish evaporators), dried by passage through a micro-
column of anhydrous sodium sulfate, and the PCB contents assayed by EC-GC.
All extraction recoveries were run in triplicate.
The PCB contents of the recovered extracts were assayed by compari-
son with the Aroclors standards. Six major peaks in the elution pattern of
Aroclor 1221 and seven major peaks for Aroclor 1254 (shown in Figure 3),
were assayed individually. The total recoveries were calculated from the
recoveries of the individual peaks. Hence both total recoveries and recov-
eries for several individual isomers (or groups of isomers where peaks repre-
sented coeluting PCBs) were determined.
12
-------
1
©
Figure 3 - Elution Patterns of Aroclor 1221 (A), 1242 (B), and 1254 (C) on an OV-210 Column
Operated Isothermally at 160, 170 and 210°C, Respectively
-------
The results of the extraction recovery studies are shown in Table
6* Recoveries were good but somewhat more variable in the case of Aroclor
1221. Part of this variability may be attributable to losses of more vola-
tile compounds during extract concentration.
TABLE 6
RESULTS OF EXTRACTION RECOVERY STUDIES
Batch Extraction Soxhlet Extraction
PCB Mixture Recovery (%) Recovery (%)
Aroclor 1221 76 + 14^ 86 ± 10
Aroclor 1254 95 ± 8 91 ± 4
a/ Standard deviations are for recoveries of all peaks in
all recovery tests.
2.2.2 Extract cleanup; The removal of interfering coextractants
is an important part of PCB analytical protocols for environmental samples.
In these studies, advantage was taken of the chemical stability of PCBs.
Since PCBs are relatively resistant to sulfuric acid, which attacks many of
the interfering materials, especially aromatics, PCB extracts in hexane were
simply shaken with concentrated sulfuric acid. The hexane solution was then
removed from the acid layer and the reacted interfering coextractants. Quan-
titative recovery of even the. more acid-susceptible monochlorobiphenyls was
demonstrated by spiking 5.0 ml portions of hexane with 2.5 yg each of £- and
p-chlorobiphenyl, shaking for 1 min with 5 ml concentrated sulfuric acid in
ftfi
a vial with a TFE -lined cap, and then assaying the chlorobiphenyls by EC-GC.
The chromatographic system described in Section 2.1.1 was utilized with the
column temperature held at 150°C. Recoveries averaged 107% for £-chlorobi-
phenyl and 105% for p-chlorobiphenyl for triplicate recovery determinations.
Although the sulfuric acid cleanup procedure is simple and allows
good recovery of PCB residues, the coextracted material in some extracts may
be acid-resistent or present in quantities too high to be removed efficiently.
In these cases, the sulfuric acid cleanup can serve as a pretreatment for more
extensive procedures such as adsorption chromatography on Florisil (60/100
mesh, PR grade). Florisil chromatography is a widely used technique for
cleaning PCB and chlorinated hydrocarbon pesticide extracts for EC-GC assays
and the procedures are described in the "Manual of Analytical Methods for
the Analysis of Pesticide Residues in Human and Environmental Samples."—'
Since these procedures have been verified and utilized by numerous investiga-
tors, no Florisil chromatographic development was included in the current
14
-------
study. The recommended protocol for extract cleanup is to treat all ex-
tracts with sulfuric acid and further clean with the Florisil procedures
where the nature and quantity of interfering coextractants require.
Some effort was devoted to the removal of biphenyl from the PCB
residues. Biphenyl can form DCB during the perchlorination of PCB residues
(as discussed in Section 2.2.3) and be included in total PCB assays. Al-
though biphenyl is a significant component of commercial PCB mixtures with
low chlorine contents, especially Aroclor 1221, its toxicity is much lower
than chlorobiphenyls. In addition, biphenyl may be present in incinerator
feed materials from sources other than"PCB residues. Unfortunately, efforts
to remove biphenyl from PCB residues were not successful.
Two widely used PCB and chlorinated pesticide cleanup techniques
were evaluated for removing biphenyl: (1) fuming sulfuric acid/sulfuric acid/
Celite column cleanup; and (2) acetonitrile/hexane partitioning. The procedures
for both techniques were as described in the "Pesticide Analytical Manual1*-'
except that hexane was substituted for petroleum ether and was used as the
eluting solvent for the acid/Celite column. Aroclor 1254, Aroclor 1221, and
biphenyl were all quantitatively (> 95%) recovered from standard solutions
cleaned by acetonitrile/hexane partitioning. Aroclor 1254 and 1221 were
spiked at 15.0 yg in their respective solutions and were assayed in the clean
solutions by EC-GC methods described in Section 2.2.1. Biphenyl was spiked
at 0.16 mg and was assayed in cleaned solutions by flame ionization GC (FID-
GC) using the same chromatographic system but with the column operated at
120°C.
Standard solutions of these same materials were also cleaned by
the fuming sulfuric acid/sulfuric acid/Celite procedure and assayed as de-
scribed above. Biphenyl could not be detected in the cleaned solutions.
Only 58.7% of the Aroclor 1221 passed the column and recoveries for the se-
lected peaks of Aroclor 1221 ranged from 2.6 to 100% with only the later
eluting peaks showing good recoveries. Aroclor 1254 was quantitatively
recovered. Hence, biphenyl can be removed by this vigorous acid treatment,
but only at the expense of losing significant quantities of the lower chlo-
rinated biphenyls.
2.2.3 Quantitation; The complex composition of PCB residues in
commercial PCB mixtures, environmental samples, and wastes complicates PCB
quantitation. Often PCB residues are quantitated by comparison of EC-GC
chromatograms with those of a commercial Aroclor mixture that is most simi-
lar. To improve comparisons the areas or heights of selected major peaks
common to the residues and the Aroclor are summed. These procedures work
well with very clean extracts where the residue closely resembles that
Aroclor. Difficulties arise in these peak summation or ."fingerprinting"
techniques when the residue does not closely resemble the particular Aroclor
15
-------
used for quantification or if interfering materials produce peaks that
coelute with the selected PCB peaks,
Chemical and/or biochemical processes can alter the composition of
PCB residues and residues may not be derived from a single commercial PCB
product. As an example, tetrachlorobiphenyls and hexachlorobiphenyls appear
to be the major contributors to PCB residues in Great Lakes fish,—' a com-
position unlike any specific Aroclor. Some methods have addressed this
problem by attempting to quantify parts of PCB residues against more than
one Aroclor for different portions of the chromatogram. However, these pro-
cedures may become both complex and subjective.
PCB residues may be quantified by GC employing electrolytic con-
ductivity detectors to gain increased specificity over electron capture de-
tection. However, problems of sorting out the composition of the residue
can still cause serious complications.
GC/MS techniques may offer the most unambiguous quantitative and
qualitative characterization of PCB residues. Operating in the selected ion
monitoring (SIM-GC/MS) mode, chromatograms of the ion intensities of ions !
characteristic of PCB isomers may be obtained .with sensitivities rivaling
EC-GC. From the ion chromatograms of two or more ions characteristics of
biphenyls with a specific number of chlorine substitutions, non-PCB inter-
ferences can be sorted out and that part of the residue quantified with the
aid of a computer.—' Unfortunately, the equipment and technological invest-
ments required for these techniques is beyond that available to many labora-
tories.
To meet the requirement of the current study for a simple total
PCB assay, results may be achieved more easily by chemical conversion of the
PCB residues to decachlorobiphenyl (DCB) and then assaying the DCB. Although
qualitative information on the composition of the PCB residues is lost, the j
residue is composited into a single compound with 10 chlorines, and more sen-j
sitivity to electron capture detection. In addition, the vigorous perchlo-
rination reaction often destroys some residual coextractants.
Exhaustive chlorination techniques for PCBs were reported by Berg
et al.,— ' refined by Armour——' and Huckins et al.,— ' and have been utilized
for PCB assays in a variety of environmental extracts. Similar procedures
have also been applied to a mixture of other chlorinated aromatics.— '
and Haile and Armstrong-Lr/ reported good correlation between assays
of fish extracts by perchlorination and peak summation techniques.
Some interferences to the perchlorination procedures have been re-
ported. Trotter and Youngi— ' found significant quantities of DCB in extracts
of several antimony pentachloride reagents. However, in the current study and
16
-------
several previous investigations, this author has not encountered reagent
blanks containing more than a few nanograms per reaction. In a recent in-
vestigation of coal extracts and gaseous emission samples (collected on
Tenax) from a coal-fired utility boiler plant, Hailei^/ found several ex-
tracts that produced DCB during perchlorination in which PCB residues could
not be confirmed by SIM-GC/MS. It was concluded that the extracts contained
large quantities of biphenyl and/or related aromatic compounds that perchlor-
inated to DCB and that GC/MS identification was necessary for verification
of PCB residues. Samples from incinerators, specifically designed to destroy
the feed material, should be much cleaner than* coal extracts or emissions
from coal-fired boilers so that perchlorination techniques for PCB analysis
should be more applicable. Nonetheless, the necessity for efficient cleanup
of extracts and PCB verification by GC/MS should not be neglected.
The basic procedure utilized in this study, adapted by
from the Armouri^/ method, involved evaporation of the cleaned extract just
to dryness in a small ('v 5-ml) culture tube. An excess of antimony penta-
chloride (0.2 ml) was added and the tubes heated to 180°C for 4 hr. The
reaction was quenched by cooling to ambient temperature and adding 2 ml of
6 N_ HC1. DCB was extracted with four "*> 1-ml portions of hexane, dried by
passage through a microcolumn (disposable pipette) of anhydrous sodium sul-
fate, and then assayed by EC-GC. Under these conditions good conversion
(85-100%) of Aroclor mixtures to DCB have been observed; however, conversions
of mono- and dichlorobiphenyls are much less and DCB yields from biphenyl are
negligible.!**/
The development of perchlorination techniques in this study was
devoted to optimizing the reaction conditions to achieve good conversion of
the lower chlorinated biphenyls. Reaction times from 1 to 4 hr and tempera-
tures from 140 to 175 °C were evaluated by perchlorinating solutions of single
chlorobiphenyl isomers. Triplicate reactions were conducted with 31 p-g of
2,2'-dichlorobiphenyl (2CB), 22.5 p,g of 2,5,2'-trichlorobiphenyl (3CB),
22.7 \Lg of 2,5,2',4'-tetrachlorobiphenyl (4CB), and 28.7 Hg of 2, 3,4, 5,6, 2', 5'-
heptachlorobiphenyl (7CB). Percent yields were calculated from the DCB
assays compared to the theoretical molar yields. The results of these eval-
uations are shown in Table 7. From these results, re,act io n .at 1 6 0° C f o r.
2 hr was_se.lected as p_roy.i.ding^the_-best-.combination of_yie,lds for these.
^ch lo ro b iphe nyls . Conversion efficiencies were also determined for Aroclor
1221., Aroclor 1254, monochlorobiphenyls, and Jbiphe.ny.l_using these conditions.
The result of evaluations (six replicates) for perchlorination under the
selected reaction conditions are summarized in Table 8. Reagent blanks for
the perchlorination reaction averaged 6 ng. The only two of the 18 blanks
ran that exceeded 10 ng were 25 and 38 ng.
17
-------
TABLE 7
YIELDS OF DCB FROM SELECTED CHLOROBIPHENYLS BY PERCHLORINATION
UNDER DIFFERENT REACTION CONDITIONS
Reaction
Temperature
Reaction
Time
(hr)
Yields of DCB (%) from
2CB 3CB 4CB
7CB
140
80.0
96.5
101
110
150
160
175
175
175
2
2
1
2
3
75.0
89.2
95.1
64.1
62.0
84.6
96.3
88.0
74.0
85.3
83.8
89.5
101
84.2
76.2
102
100
88.9
82.0
86.6
175
75.7
72.2
86.0
82.0
TABLE 8
PERCENT YIELDS OF DCB FROM CHLOROBIPHENYLS BY PERCHLORINATION
AT 160°C FOR 2 HR
Chlorobiphenyl
Biphenyl
o-lCB
2-1CB
2CB
3CB
4CB
7CB
Aroclor 1221
Aroclor 1242
Aroclor 1254
Weight Added
(yg)
4.9
5.0
5.0
31.0
22.5
22.7
28.7
0.64
1.0
0.58
Yield of DCB
61.2
76.8
42.5
89.2
96.3
89.5
100
80.2
84.1
82.1
18
-------
Since the lower chlorinated biphenyls generally exhibited lower
DCS yields from perchlorination, the possible loss of these more volatile
PCBs during evaporation of the extracts was investigated. Aliquots of hex-
ane (5 ml) in the culture tubes were spiked with 5 yg of each monochloro-
biphenyl, evaporated just to dryness with a gentle stream of dry nitrogen,
redissolved in 5.0 ml of hexane, and assayed by EC-GC. Recoveries following
evaporation were 84.8 and 81.5% for the ortho and para isomers, respectively.
Hence losses from evaporation likely contribute to the lower DCB yields of
monochlorobiphenyls, but not markedly so.
Some investigators have reported good DCB yields by slowly heat-
ing the reaction mixture to temperature and allowing the reaction to con-
tinue overnight. Limited exploration of this procedure with Aroclor 1221
and 1254 standards resulted in yields of 76.1 and 76.8%, respectively, for
the two Aroclors. These yields are 4 to 5% less than obtained from 2-hr
reactions.
19
-------
3.0 EVALUATION OF THE PCB METHOD FOR INCINERATORS
3.1 Laboratory Evaluation of Sampling Train Efficiency
The selected sampling system was subjected to extensive laboratory
evaluation to determine coJLlection efficiency. Sampling trains were assembled
and operated in the laboratory by procedures similar to those used in field
sampling. After the trains were leak checked, without a probe, sample intro-
duction tubes, similar to that described in Section 2.1.1, were attached.
Sampling tests were run at a flow rate of 20 liters/min for 4 hr. During each
30 min period of the tests, an aliquot (10-25 u.1) of an Aroclor standard so-
lution (Aroclor 1221, 1242, or 1254) in hexane was added to the depression
in the sample introduction tube. The PCB spikes were volatilized into the
sample stream with a heat gun. After completion of the test runs, the trains
were disassembled and the sample recovered according to the preliminary method.
The adsorbent tubes and impinger contents were extracted, train rinsings were
added to the impinger extracts, and the extracts concentrated. Extracts were
not cleaned up but were assayed directly by EC-GC comparison with the appro-
priate Aroclor by procedures described in Section 2.2.1. Six major peaks in the
elution pattern of Aroclor 1221, nine major peaks for Aroclor 1242, and seven
major peaks for Aroclor 1254 (see Figure 3) were selected for quantification.
The results of these tests are shown in Table 9.
The distribution of the PCBs in the impinger and adsorbent sections <
of the trains was quite interesting. The earlier eluting, and likely more '
volatile, PCB compounds were generally recovered from the Florisil adsorbent
(evidently easily passing through the series of impingers), while the later
eluting PCBs were more likely to be recovered from the impingers. Typically
all of the Aroclor 1221 and nearly all of the Aroclor 1242 was recovered
from the Florisil. The seven peaks of Aroclor 1254 were generally distribu-
ted in both portions of the train. Table 10 shows the distribution from a
typical test run.
Although XAD-2 had been abandoned as an adsorbent alternative in
the preliminary tests (Section 2.1.1), a specially prepared sample (received
from Dr. Phillip Levins, A. D. Little, Inc.) was evaluated as a part of the
selected PCB train. The resin had been prepared by an extensive series of
exhaustive Soxhlet extractions with water, methanol, diethyl ether, and
pentane.Z' A train with 5.7 g XAD-2 tube recovered 88% of the spiked Aroclor
1221 when evaluated as described above. However, because of the rather
involved resin preparation required, Florisil was retained as the selected
adsorbent.
20
-------
TABLE 9
SAMPLING EFFICIENCY OF PCB SAMPLING TRAIN
Peak No.
2
3
4
5
6
7
Mean
PCB Mixture Total Spike Recovery^'
(us) (%)
Aroclor 1221 23.8 86+9
Aroclor 1242 18.2 88 + 10
Aroclor 1254 11.6 92+3
a/ Average and standard deviation for six tests.
TABLE 10
DISTRIBUTION OF AROCLOR 1254
SPIKE IN THE SAMPLING TRAIN
Recovery in Impingers Recovery in Adsorbent Total
(%) (%)
22.9 75.2
32.3 57.8
39.7 50.6
63.5 31.1
77.3 21.6
82.6 14.3
81.1 11.1
Recovery
(%)
98.1
90.1
90.3
94.6
98.9
96.9
92.9
94.4
21
-------
3.2 Field Evaluations
The PCB sampling and analysis method was also evaluated by testing
at two municipal sewage sludge incinerators, two industrial incinerators, and
five municipal refuse incinerators. In all tests, two identical trains were
operated simultaneously to aid evaluation of the precision of the method.
The PCB results of all tests are expressed as DCB and were not corrected
for perchlorination efficiency.
3.2.1 Municipal sewage sludge incinerators; Emissions were sam-
pled from sewage sludge incinerators at municipal sewage treatment facilities
in the Kansas City, Missouri area. The Blue River facility of the City of
Kansas City, Missouri, receives wastes with a significant industrial compo-
nent while the facility of the City of Mission, Kansas, receives mostly do-
mestic wastes. Sludges are dewatered by vacuum filtration in both plants
prior to incineration. Both incinerators operate under induced draft and
employ a wet scrubber for air pollution control. The Mission, Kansas, in-
cinerator is diagrammatically represented in Figure 4.
Table 11 summarizes the test data and PCB results for testing of
outlet flue gases for both incinerators. Extracts of all samples from the
incinerators required cleanup by chromatography on Florisil in addition to
sulfuric acid cleanup to remove interfering coextractants. The Blue River
samples contained much higher levels of PCBs.
3.2.2 Industrial incinerators: Two incineration plants, designed
and operated for contract incineration of industrial wastes, were sampled dur-
ing staged test burns of PCB-containing wastes. The two incinerators were
designed and operated quite differently. The Rollins Environmental Services
facility in Deer Park, Texas, diagrammatically represented in Figure 5, burns,
solid wastes and is primarily fired with petroleum-based fuels. Wastes are con-
veyed into a rotary ignition chamber. The plant employs an afterburner and a
wet scrubber to achieve high efficiency combustion and control emissions. Dur-
ing the first day of testing ground capacitors, containing >vL7% PCB fluids,
were combusted. Whole capacitors were burned during the second day of testing.
The second industrial incinerator, to be identified only as Plant B
herein, handles liquid wastes and is fired with the wastes only. The composi-
tion of the wastes, largely petroleum-based solvents, was adjusted to optimize
incineration. During tests, liquid wastes containing approximately 10%
PCB fluids, estimated by the plant operators, were incinerated. Emissions
control was with a packed-tower scrubber.
The results of these tests are summarized in Table 12. Only three
samples were collected at the Rollins incinerator. Samples 1A and IB were
taken during the burn of ground capacitors and 2A was collected during the
burn of whole capacitors. Unfortunately, excessive breakage of train com-
ponents in shipping prevented assembly and sampling to duplicate the 2A
sample.
22
-------
Temp.
Control
Damper
\
4 Hearth
Furnace
1
Cool Air
I
• Sampling Port
I.D. Fan
Scrubber
Roof
Figure 4 - Schematic Illustration of the Mission, Kansas
Sewage Sludge Incinerator
23
-------
TABLE 11
ro
Incinerator
Run Number
Date
Sampling Location
SUMMARY OF PCB RESULTS (AS DCB) FOR TWO SEWAGE SLUDGE INCINERATORS
Blue River (Kansas City), MO
Mission. KS
a/
—
Volume of gas sampled (dscf)—
3. /
Volume of gas sampled (dscm)—
Percent moisture
Flue gas temperature (°F)
Feed rate (Ib/hr)
Total PCBs in sample (p,g, as DCB)
PCB concentration in sample
(10 grains/dscf, as DCB)
PCB concentration in sample
(Hg/dscm, as DCB)
Average PCB concentration in
sample (y,g/dscm, as DCB)
1
10/11/76
Outlet
118.4
3.35
15.8
y
--
1022
133
2
10/11/76
Outlet
95.6
2.71
17.3
y
--
836
135
3
10/11/76
Outlet
82.8
2.35
13.6
y
--
674
126
4
10/11/76
Outlet
83.8
2.37
13.0
y
--
233
42.9
1A
4/12/76
Outlet
104.0
2.95
11.1
140
1463
11.3
1.7
IB
4/12/76
Outlet
99.7
2.82
8.8
140
1463
10.6
1.6
305
306
308
287
98
192
3.80
3.70
3.75
a/ dscf = dry standard cubic foot
dscm = dry standard cubic meter
b/ Not recorded
-------
Stack
Scrubber Afterburner
Rotary
Ignition
Chamber
T
-50'
Ports
o o
Inlet
Conveyor
Belt
PLAN VIEW
Figure 5 - Schematic Illustration of the Rollins, Inc., Industrial
Incinerator, Deer Park, Texas
25
-------
TABLE 12
10
SUMMARY OF PCB RESULTS (AS. DCS) FOR TWO INDUSTRIAL INCINERATORS
Incinerator
Run Number
Date
Sampling Location
Volume of gas sampled (dscf)~
Volume of gas sampled (dscm)—'
Percent moisture
Flue gas temperature (°F)
Feed rate (gal/hr)
Total PCBs in sample (ug as DCB) 1.42 x 10"3
PCB concentration in sample
(10~ grains/dscf, as DCB)
Rollins, Inc. (Deer Park, TX)
1A
12/8/76
Outlet
62.33
1.76
34.1
130
42 x 10'3
0.35
IB
12/8/76
Outlet
61.52
1.74
33.3
130
1.18 x 10'3
0.30
2A*/
12/9/76
Outlet
75.40
2.13
35.2
130
3.9 x ID'3
0.80
Industrial Incinerator B
1A
3/15/66
Outlet
117.7
3.33
14.0
122
450
0.789
103
IB
3/15/77
Outlet
24.3
0.69
1.9^
122
450
0.283
180
2A
3/16/77
Outlet
134.3
3.80
\.&J
147
450
0.226
26.0
2B
3/16/77
Outlet
137.17
3.88
2.3^
147
450
0.349
39.3
PCB concentration in sample
(Hg/dscm, as DCB)
Average PCB concentration in
sample (^g/dscm, as DCB)
0.79 x 10
-3
0.69 x 10'3 1.83 x 10"3 237x10
,-3
410 x 10
-3
0.74 x 10
-3
324 x10-3
59.0xlO"3 90.0xlO~3
74.5xlQ-3
aj Run 2B was disabled by breakage
b_/ dscf = dry standard cubic foot
dscm = dry standard cubic meter
c/ Percents of moisture for these runs are questionable
-------
Although the moisture content of flue gases from the Rollins plant was high,
the test burns only allow sampling for less than 2 hr and water accumulation
in the impingers was not excessive.
Sample extracts from these incinerators were rather clean so that
sulfuric acid treatment was sufficient to remove interfering materials. The
efficiencies of these incinerators was demonstrated by the lowest PCB con-
centrations sampled.
3.2.3 Municipal refuse incinerators; Five municipal refuse incin-
erators in the Miami-Ft. Lauderdale (FL) area were sampled for PCB emissions
for purposes of method evaluations. Both inlet and outlet samples were col-
lected at three incinerators.
Outlet samples were collected from the Miami incinerator No. 1, diagram-
matically represented in Figure 6, The incinerator was operated under induced
draft and utilized a water sprayer for pollution control. Municipal refuse is
fed in a batch mode.
The Bade Co., N.E. incinerator was tested during evaluations of pre-
liminary train designs, described in Section 2.1.2. A schematic illustration
of the incinerator, which operates under induced draft, is shown in Figure 7.
Flue gas samples were collected after the electrostatic precipitator.
Both inlet and outlet samples were collected from the No. 1 (South
Side) and No. 2 incinerators at the Broward Co. Plant No. 1 in Ft. Lauderdale.
Incinerator No. 2 operates in the batch mode. Both incinerators operate with
induced draft and utilize scrubbers for pollution control. The design of
Incinerator No. 1 is shown in Figure 8. Figures 9 and 10 show the design
of Incinerator No. 2 and the location of inlet and outlet sampling points,
respectively. Inlet and outlet samples were also collected from the Broward
Co. Plant No. 2, Incinerator No. 4, in Pompano Beach. This incinerator is
diagrammatically represented in Figure 11.
The results of the method evaluation testing at municipal refuse
incinerators are summarized in Table 13. The method was modified for inlet
sampling by using a water-cooled stainless steel probe to withstand the high
flue gas temperatures of these samples. During two of the runs at the Broward
Co. Plant No. 1, Incinerator No. 1, the impingers filled with condensed water
such that it splashed onto the Florisil. In these cases the runs were ter-
minated because of the excessive pressure drops across the trains. Subse-
quent sampling at Incinerator No. 2 and Plant No. 2, Incinerator No. 4 was
conducted with two additional empty impingers connected in series just in
front of the adsorbent tube to collect water. Part A of the proposed method
was appended to accommodate this special case.
27
-------
From a Second
Incinerator
Sampling
Port
Water
Sprayer
From
Incinerator
Figure 6 - Schematic Illustration of the Miami (FL) No. 1
Municipal Incinerator
28
-------
|| Sampling
Port
From Incinerator
Figure 7,"- Schematic Illustration of Dade Co. (FL), N.E.
Municipal Incinerator
29
-------
Figure 8 - Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 1
(South Side)
Outlet
'Sampling
Port
u>
o
Inlet Sampling Port-
Furnace
O
Scrubber
I.D. Fan
Stack
-------
Refuse In
J
Residues
Out
Furnace
D
'Secondary Combustion
Chamber
Scrubber
Stack
Truck
\ /
Inlet Sampling Port |.D. Fan
Figure 9 - Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 2 (Batch),
Inlet
31
-------
Stack
From Incinerator
tScrubber
Flow
O Outlet
O Sampling
O Ports
Flow
Figure 10 - Schematic Illustration of Broward Co. Plant No. 1,
Ft. Lauderdale, Florida, Incinerator No. 2 (Batch),
Outlet
32
-------
Roof
Co
Outlet
Sampling
Port
Water Pipes
I.D. Fan
Scrubber
-©-
Inlet Sampling
-Port
Furnace
Figure 11 - Broward Co. Plant No. 2, Pompano Beach, Florida,
Incinerator No. 4
-------
TABUS 13
SUMMARY OF FOB RESULTS (AS DCB) FOR FIVE MUNICIPAL REFUSE INCINERATORS
Miami (FL) No. 1
Incinerator
Run Number
Date
Sampling Location
Volume of gas sampled (dscf)—
Volume of gas sampled (dscm)—'
Percent moisture-
Flue gas temperature (°F)
Feed Rate (ton/hr)
Total PCBs in sample (u,g, as DCB)
PCB concentration in sample
(10~6 grains/dscf, as DCB)
PCB concentration in sample
(Hg/dscm, as DCB)
Average PCB concentration In
sample (ng/dscm, as DCB)
(Batch)
1A
1/18/77
Outlet
92.95
2.63
9.6
300
12
93.8
15.5
35.5
33.
IB
1/18/77
Outlet
91.49
2.59
9.6
300
12
83.5
14.0
32.0
,8
Dade Co.
2A
1/19/77
Outlet
86.44
2.45
13.4
460
12
34.1
6.1
13.9
10.
(FL), NE
2B
1/19/77
Outlet
83.38
2.36
8.9
460
12
15.5
2.9
6.6
3
Broward Co. (FL) Plant No. 1, Ft. Lauderdale
No. 1 South Side
3A1
1/21/77
Inlet
46.01
1.30
20.3
1800
9
15.6
5.2
11.9
13
3B1
1/21/77
Inlet
44.81
1.27
21.0
1800
9
19.2
6.6
15.1
.5
3A1
1/21/77
Outlet
132.7
3.76
29.2
155
9
8.40
1.0
2.3
2.
3B1
1/21/77
Outlet
138.7
3.93
14.8
155
9
8.40
0.9
2.0
,2
No. 2 (Batch)
3A2
1/24/77
Inlet
60.74
1.72
3.2
1400
5
8.97
2.3
5.3
5.
3B2
1/24/77
Inlet
68.19
1.93
14.2
1400
5
6.22£/
,3
3A2
1/24/77
Outlet
82.08
2.32
20.5
135
5
9.48
1.8
4.1
5.
3B2
1/24/77
Outlet
79.17
2.24
19.6
5
15.7
3.0
6.9
5
Broward Co. (FL) Plant No. 2
Pompano Beach No. 4
4A
1/25/77
Inlet
62.20
1.76
2.5
540
6
16.5
4.1
9.4
7.
4B
1/25/77
Inlet
65.80
1.86
13.1
540
6
10.4
2.4
5.5
.5
4A
1/25/77
Outlet
122.0
3.45
18.5
430
6
10.2
1.3
3.0
3.
4B
1/25/77
Outlet
125.7
3.56
15.5
430
6
14.2
1.7
3.9
,5
a/ dscf = dry standard cubic foot
dscm = dry standard cubic meter
b/ Flue gases of runs 3A1 outlet, 3A2 outlet, and 3B2 outlet were supersaturated with water. Moisture contents of runs 361 outlet, 3A2 Inlet, and 5A inlet are questionable
and were not considered in subsequent calculations.
£/ The impinge extract was lost for this run so the results were not averaged.
-------
Sample extracts from all municipal refuse incinerators required the
additional cleanup of the Florisil chromatography procedure. The impinger
extract of sample 3B2 outlet was lost so that the assay for this sample re-
flects only the contents of the adsorbent tube.
3.2.4 Results of field evaluations; In the course of the field
evaluations, samples were collected from supersaturated flue gases and flue
gases as hot as 1800°F. PCB residues (as DCB) ranging from ~ 1 ng to ~ 1 mg,
corresponding to concentrations of < 1 ng/dscm and 306 |ig/dscm, respectively,
were determined. The mean percent deviation from the average for paired
train samples was 13 + 10% for all tests excluding runs 3 and 4 for the
Blue River incinerator and runs 2A and 2B for the Dade Co. (NE) incinerator.
PCB isomers were identified in all of the samples examined by GC/MS (approx-
imately 50% of the total samples). The PCB verifications are described in
Section 3.3.
3.3 Confirmation of PCS Residues from Incinerators
PCB residues were verified in all of the more than 50% of the in-
cinerator samples examined. Extracts were concentrated to 1 ml by evaporation
with a gentle stream of dry nitrogen prior to SIM-GC/MS examination. The
chromatographic system utilized was that described in Section 2.1.1. Inten-
sities of ions characteristic of PCB compounds were monitored. Coincident
peaks in the ion chromatograms with relative intensities corresponding to those
of the PCB compounds and at appropriate retention times were criteria for PCB
verification. As examples of the verification, chromatograms for Aroclor
1254, Sample 2A from the Rollins, Inc., industrial incinerator, and Sample 2
from the Blue River sewage sludge incinerator are shown below.
Figures 12, 13, and 14 show SIM-GC/MS chromatograms for Aroclor
1254. Tetrachlorobiphenyls are shown in the plots of m/e 290 and 292 in Fig- ';
ure 12. Peaks eluting prior to ~ 2.5 min represent the tetrachlorobiphenyls. I
Peaks eluting after 2.5 min likely represent hexachlorobiphenyls since m/e
290 and 292 are prominent fragment ions in their mass spectra. Figure 13, j
chromatograms for m/e 324 and 326, shows the presence of pentachlorobiphenyls
in Aroclor 1254 and Figure 14 shows hexachlorobiphenyls. Note the coincidence
of the hexachlorobiphenyl peaks with the later eluting peaks in Figure 12.
The SIM-GC/MS chromatograms for Sample 2A from the Rollins, Inc.,
industrial incinerator are shown in Figures 15, 16, and 17. The peaks eluting
at ~ 0.8 min on the m/e 290 and 292 plots (Figure 15) do not represent a tetra-
chlorobiphenyl since the ratio of ion intensities is not correct. However,
peaks on the other plots (Figures 15, 16, and 17) indicate the presence of
several tetra-,. penta-, and hexachlorobiphenyls.
SIM-GC/MS chromatograms of the impinger extract from Sample 2 from
the Blue River incinerator are shown in Figures 18, 19, and 20. Tetra- and
pentachlorobiphenyls were identified along with a trace of hexachlorobiphenyl.
35
-------
M..-E 29$ 50:;
(A)
SOX
M.-'E 292 5QX
UJ
234
MINUTES
(B)
50X
..1 23 4 5 6
MINUTES
Figure 1Z - SIM-GC/MS Chromatograms of m/e 290 (A) and
292 (B) for 2.0 ng Aroclor 1254
36
-------
324 M "E
(A)
1 - 1 - - 1 - 1
1 - 1
3
MINUTES
n—l~~r
5
1 I ' '
6
M-'E 326 SOX
(B)
• 50X
123^56
MINUTES .-•'.'..-
Figure 13 - SIM-GC/MS Chromatograms of m/e 324 (A) and
326 (B) for 2.0 ng Aroclor 1254
37
-------
M.-'E 3*0 5Qi"'X
(A)
500X
T I | I I |
1 2
I I | I I
3
MINUTES
| i i |
5 6
N-'E 362 200, 5yCX
(B)
ul
I ' ' I ' ' I
234
MINUTES
I
3
500X
200X
Figure 14 - SIM-GC/MS Chromatograms of m/e 360 (A) and 362 (B)
for 2.0 ng Aroclor 1254
38
-------
M.--E 290 £5X
(A)
CO
25X
I
5
I
6
MINUTES
M/E 2?2
V
t—
I-*
CO
(B)
25X
1 I ' ' I T ^ I r ^ 7 ' r I ' ' I ' '
123456
: MINUTES
Figure 15 - SIM-GC/MS Chromatograms of m/e 290 (A) and 292 (B)
for Sample 2A from the Rollins Industrial Incinerator
39
-------
M-'E 324 i^>:
(A)
Ld
-i 1 1 . 1 1 r
1
i ' ' i '—r~r
2345
MINUTES
25X
M-'E 326 £5X
(B)
LJ
' I '
3
MINUTES
I
5
I
6
Figure 16 - SIM-GC/MS Chromatograms of m/e 324 (A) and
326 (B) for Sample 2A from the Rollins Industrial
Incinerator
40
25X
-------
M-'E 360 5u. tOOX
(A)
M-'E 362 166X
(B)
100X
I . . I I I I
234
MINUTES
I
5
I
6
Figure 17 - SIM-GC/MS Chromatograms of m/e 360 (A) and 362 (B) for
Sample 2A from the Rollins Industrial Incinerator
41
-------
M/E 233 1Q.. 25X
(A)
fVE 232 25X
(B)
25X
I
3
MINUTES
I
5
I
6
Figure 18 - SIM-GC/MS Chromatograms of m/e 290 (A) and 292 (B)
for Sample 2 from the Blue River Sewage Sludge Incinerator
42
-------
M.--E 324 sex
nI r
1
(A)
2 3
MINUTES
SOX
I I I I I
M/E 326 59X
UJ
I
2
(B)
1 I '
3
MINUTES
SOX
Figure 19 - SIM-GC/MS Chromatograms of m/e 324 (A) and 326 (B)
for Sample 2 from the Blue River Sewage Sludge Incinerator
43
-------
74x7 M/E 368 160X
74/8 M/E 362 1Q9X
UJ
m/e 362
r^ T I T ' i • ' I f f i f • I
1 2 34 » 6
MINUTES
Figure 20 - SIM-GC/MS Chromatogram of m/e 360(A) and 362(B) for
Sample 2 from the Blue River Sewage Sludge Incinerator
-------
4.0 APPLICATION OF THE PCB METHOD TO EMISSIONS FROM CAPACITOR- AND
TRANSFORMER-FILLING PLANTS
4.1 Method Adaptation
Gaseous emissions from capacitor- and transformer-filling plants
are generally much easier to sample for PCB residues than emissions from
incineration plants. Air is exhausted from filling rooms at temperatures
and moisture contents near ambient and is less likely to contain excessive
quantities of other organics. For these cases, the sampling train was sim-
plified by removing the water-cooled probe and ice-cooled impingers. Hence,
the sampling train was reduced to merely the adsorbent tube with associated
pump and metering system and provisions for attaching a simple glass-lined
probe to facilitate sampling of exhaust ducts. The simplicity of the sam-
pling equipment allows elimination of sample recovery in the field. Suffi-
cient adsorbent tubes and probes (where applicable) can be shipped to and
from the sampling site to reduce chances of contamination during field sam-
ple recovery. Since the PCB residue collected may often closely resemble
the particular commercial PCB mixture employed in the plant operations, the
sampled residue may be quantitated against standard solutions of the appro-
priate commercial PCB mixture. In the event that the sampled residue does
not closely resemble the mixture used in the plant, total PCBs may be as-
sayed by the perchlorination procedures described for incinerator PCB resi-
dues. These modifications of the incinerator method are described in Part
B of the appendix to this report.
4.2 Field Evaluations
The proposed PCB method for emissions from capacitor- and trans-
former-filling plants was evaluated by testing at two capacitor-filling plants
herein designated A and B. For the purposes of these evaluations the ambient
air in the filling rooms were sampled rather than exhausted air. The sampling
systems were operated in tandem, positioned between the capacitor impregnation
tanks, to provide duplicate samples. Sampling was conducted at 14 liters/min
for 30 min to 4 hr to obtain a range of amounts of PCBs sampled. To check for
PCB breakthrough, one of each of the duplicate trains utilized at Plant B was
fitted with an additional Florisil tube connected in series to the primary ad-
sorbent tube. For evaluation purposes, all samples from both plants were
assayed by the perchlorination procedure.
The results of these field evaluation tests are shown in Table 14.
The PCB residues recovered from the second Florisil tubes of Samples 1A, 2A,
and 3A from Plant B contained 0.05, 0.15, and 0.1% of the total residue col-
lected from those samples. Even when sampling milligram quantities of PCBs
at 14 liters/min over 2 hr, breakthrough of the PCBs was negligible. The aver-
age percent deviation from the mean for the paired trains was 1.5% for Plant A
when the large deviation of Samples 2A and 2B was ignored. The average percent
45
-------
TABLE 14
SUMMARY OF PCB RESULTS (AS DCB) FOR TWO CAPACITOR-FILLING PLANTS
Plant: A B
Run Number: 1A IB 2A 2B 3A 3B 1A IB 2A 2B 3A 3B
Date: 2/7/77 2/7/77 2/8/77 2/8/77 2/8/77 2/8/77 2/15/77 2/15/77 2/15/77 2/15/77 2/15/77 2/15/77
Time: 13:00-17:00 13:00-17:00 7:00-9:00 7:00-9:00 9:05-10:05 9:05-10:05 7:10-9:10 7:10-9:10 9:15-10:15 9:15-10:15 10:20-10:50 10:20-10:20
Sampling period (hr) 4.0 4.0 2.0 2.0 1.0 1.0 2.0 2.0 1.0 1.0 0.50 0.50
Volume of gas sampled 3.29 3.29 1.69 1.69 0.836 0.836 1.66 1.66 0.830 0.830 0.414 0.414
(scm)S/
Total PCBs tn sample 2,750 2,940 467.2 96.0 332.8 332.9 4,610 3,840 1,090 2,180 1,020 2,130
(Hg, as DCB)
PCB concentration In 835 892 276 56.9 398 399 2,770 2,310 1,310 2,630 2,460 5,150
sample (lig/scra, as DCB)
Average PCB concentra- 864 166 399 2,540 1,970 3,810
-p- tlon in sample (|ig/
& son, as DCB)
a/ sera = Standard cubic meter.
-------
deviation was 26% for Plant B samples, likely reflecting the error introduced
in several dilutions of the extracts to obtain concentrations appropriate for
EC-CG assay. Both plants could have been adequately sampled for shorter
periods with lower sampling rates if challenging the method had not been the
primary objective.
The variation in the samples from Plant A likely reflect the actual
production operations. Whereas Plant B was operated 24 hr daily, Plant A was
operated by a single 8-hr shift each day. Samples 2A and 2B were taken at the
beginning of the shift while capacitor impregnation operations were being ini-
tiated. Samples 3A and 3B were taken during mid-morning and 1A and IB were
taken during mid to late afternoon and included the period during which the
impregnation equipment was cleaned in preparation for cessation of operations
for the day.
47
-------
5.0 CONCLUSONS
The adaptation of the Method 5 train by removing the heated filter
and adding an adsorbent tube produced an efficient, simple, and compact sampl-
ing system for determining PCB emissions from industrial, sewage sludge, and
municipal refuse incinerators. Of the three solids evaluated as a PCB ad-
sorbent, 30/60 mesh Florisil was selected over Tenax-GC and XAD-2 based on
trapping efficiency and the preparations required to obtain acceptable blanks.
From laboratory studies, sampling efficiencies of 86 to 92% for Aroclors
were determined for the sampling train using Florisil.
The sample recovery and PCB analysis protocol developed was based
on procedures widely used for PCB residues in environmental samples. PCB
samples collected were perchlorination to decachlorobiphenyl (DCB) and the
DCB assayed. Molar yields of DCB from Aroclor mixtures were generally 80
to 85%. '
The method was tested by sampling nine incineration plants. Since
inlet and outlet samples were collected, a wide variety of flue gases were
encountered, including gases as hot as 1800°F and gases saturated with
moisture. PCB concentrations ranging from 1 ng/dscm to > 300 ^g/dscm (as
DCB) were determined. The mean percent deviation from average determinations
for duplicate samples was 13 + 10%. The presence of PCB isomers was verified
by SIM-GC/MS in all of the more than 50% of the samples examined.
The PCB method was modified to allow determination of PCB emissions
from capacitor- and transformer-filling plants. The sampling train was modi-
fied by removing the ice-cooled impingers. The modified method was tested by
sampling ambient air in impregnation rooms of two capacitor-filling plants.
PCB levels ranging from 166 to > 2,500 ^g/m (as DCB) were determined.
Milligram quantities of PCBs were collected in some samples. PCB breakthroughs
of < 0.15% were determined for the Florisil adsorbent tube by sampling with
two tubes connected in series.
Overall, this study demonstrates the suitability of 30/60 mesh
Florisil for collecting PCB residues from a variety of airstreams and
suggests an applicability to PCB sampling of ambient air that should be
investigated.
The PCB method developed is contained in an appendix to this report.
48
-------
6.0 LITERATURE CITED
1. Environmental Protection Agency. 1976. Polychlorinated Biphenyl-
Containing Wastes, Disposal Procedures. Federal Register. 41^:14134-
14136.
2. Margeson, J. H. 1977. Methodology for Measurement of Polychlorinated
Biphenyls in Ambient Air and Stationary Sources--A Review. Environ-
mental Monitoring Series, EPA-600/4-77-021, Environmental Protection
Agency, 31 pp.
/3.' Giam, C. S., H. S. Chau, and G. S. Neff. 1975. Rapid and Inexpensive
Method for Detection of Polychlorinated Biphenyls and Phthalates in
Air. Anal. Chem.. 47^:2319-2320.
4./ Adams, J., K. Menzies, and P. Levins. 1977. Selection and Evaluation
^~~ of Sorbent Resins for the Collection of Organic Compounds. Interagency
Energy-Environment Research and Development Program Report, EPA-600/7-
77-044, Environmental Protection Agency, 61 pp.
5. Jones, P. W., R. D. Glammer, P. E. Strup, and T. B. Stanford. 1976.
Efficient Collection of Polyeyelie Organic Compounds From Combustion
Sources. Environ. Sci. Techno1. 10:806-810.
6. Neher, M. B., and P. W. Jones. 1977. In Situ Decomposition Product
Isolated From Tenax GC® While Sampling Stack Gases. Anal. Chem.
49^:512-513.
<7,. Thompson, J. F. (ed.). 1974. Analysis of Pesticide Residues in Human
and Environmental Samples. Environmental Protection Agency, Research
Triangle Park, N.C.
Food and Drug Administration. 1972. Pesticide Analytical Manual. Food
and Drug Administration, Rockville, MD.
9. Haile, C. L0, D. E. Armstrong, and D. Kuehl. 1977. GC/MS Examination
of Fish Extracts From Lake Ontario and Lake Michigan. In preparation.
10. Cairns, T., and E. G. Siegmund. 1977. Polychlorinated Biphenyl (PCB)
Quantitation by Chemical lonization GCMS. Presented to Twenty-Fifth
Annual Conference on Mass Spectrometry and Allied Topics, American
Society for Mass Spectrometry, Washington, D.C.
49
-------
~^11. Berg, 0. W., P. I. Diosady, and G. A. V. Rees. 1972. Column Chromato-
graphic Separation of Polychlorinated Biphenyls From Chlorinated Hy-
drocarbon Pesticides and Their Subsequent Gas Chromatographic Quanti-
tation in Terms of Derivatives. Bull. Environ. Contam. Toxicol. !_•
338-347. ""
"^ 12. Armour, J. A. 1972. Quantitative Perchlorination of Polychlorinated
Biphenyls as a Method for Confirming Residue Measurement and Identi-
fication. J.A.O.A.C. 56^:987-993.
13. Huckins, J. N., J. E. Swanson, and D. L. Stalling. 1974. Perchlorina-
tion of Polychlorinated Biphenyls. J.A.O.A.C. 57^:416-417.
J&» Hutzinger, 0., W. D. J. Jamieson, S. S. Safe, and V. Z. Zitko. 1973.
Exhaustive Chlorination as a Technique in the Analysis of Aromatic
Hydrocarbons. J.A.O.A.C. 56:982-986.
15'. Veith, G. D. 1975. Baseline Concentrations of Polychlorinated Biphenyls
and DDT in Lake Michigan Fish, 1971. Pestic. Monit. J. 9:21-29
.. Haile, C. L., and D. E. Armstrong. 1977. DDT, Dieldrin, and PCB Resi-
"—^ dues in the Southern Lake Michigan Ecosystem--1974. In preparation.
17. Trotter, W. J., and S. J. V. Young. 1975. Limitation of the Use of
Antimony Pentachloride for Perchlorination of Polychlorinated Bi-
phenyls. J.A.O.A.C. 58:466-468.
•i Haile, C. L. 1976. PCB Interlaboratory Verification Analysis. Final
Report to Environmental Protection Agency, Contract No. 68-02-1399,
22 pp.
50
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APPENDIX
(DRAFT METHOD)
DETERMINATION OF TOTAL POLYCHLORINATED BIPHENYL (PCB)
EMISSIONS FROM STATIONARY SOURCES
51
-------
PART A. INDUSTRIAL, SEWAGE SLUDGE, AND
MUNICIPAL REFUSE INCINERATORS
1. Principle and Applicability
1.1 Principle. Gaseous and particulate PCBs are withdrawn isokinet-
ically from the source using a sampling train. The PCBs are collected in
the Florisil adsorbent tube and in the impingers in front of the adsorbent.
The total PCBs in the train are determined by perchlorination to decachloro-
biphenyl (DCB) and gas chromatographic determination of the DCB.
1.2 Applicability. This method is applicable for the determination
of PCB emissions (both vaporous and particulate) from industrial, sewage
sludge, and municipal refuse incinerators.
2. Range and Sensitivity
The range of the analytical method may be expanded considerably
through concentration and/or dilution. The total method sensitivity is also
highly dependent on the volume of gases sampled. However, the sensitivity of
the total method as described here is about 10 ng DCB for each analytical .
replicate.
3. Interferences
Excessive quantities of acid-resistant organics may cause signifi-
cant interferences obscuring the analysis of DCB in the perchlorinated ex-
tracts. Biphenyl, although unlikely to be present in samples from combus-
tion sources, can form DCB in the perchlorination processes.
Throughout all stages of sample handling and analysis, care should
be taken to avoid contact of samples and extracts with synthetic organic
materials other than TFE® (polytetrafluoroethylene). Adhesives must not be
used to hold TFE® liners on lids, and lubricating and sealing greases must
not be used on any sample exposed portions of the sampling train.
4. Precision and Accuracy
From sampling with identical and paired sampling trains, the pre-
cision of the method has been determined to be 10 to 15% of the PCB concentra-
tion measured. Recovery efficiencies on source samples spiked with PCB com-
pounds ranged from 85 to 95%.
52
-------
5. Apparatus
5.1 Sampling Train. See Figure A-l; a series of four impingers with a
solid adsorbent trap between the third and fourth impingers. The train may
be constructed by adaptation from a Method 5 train. Descriptions of the
train components are contained in the following subsections.
5.1.1 Probe nozzle—Stainless steel (316) with sharp, tapered
leading edge. The angle of taper shall be £ 30 degrees and the taper shall
be on the outside to preserve a constant internal diameter. The probe noz-
zle shall be of the button-hook or elbow design, unless otherwise specified
by the Administrator. The wall thickness of the nozzle shall be less than
or equal to that of 20 gauge tubing, i.e., 0.165 cm (0.065 in.) and the dis-
tance from the tip of the nozzle to the first bend or point of disturbance
shall be at least two times the outside nozzle diameter. The nozzle shall
be constructed from seamless stainless steel tubing. Other configurations
and construction material may be used with approval from the Administrator.
5.1.2 Probe liner--Borosilicate or quartz glass equipped with a
connecting fitting that is capable of forming a leak-free, vacuum tight con-
nection without sealing greases; such as Kontes Glass Company "0" ring spher-
ical ground ball joints (model K-671300) or University Research Glassware SVL
teflon screw fittings.
A stainless steel (316) or water-cooled probe may be used for sam-
pling high temperature gases with approval from the Administrator. A probe
heating system may be used to prevent moisture condensation in the probe.
5.1.3 Pitot tube—Type S, or equivalent, attached to probe to
allow constant monitoring of the stack gas velocity. The face openings of
the pitot tube and the probe nozzle shall be adjacent and parallel to each
other but not necessarily on the same plane, during sampling. The free
space between the nozzle and pitot tube shall be at least 1.9 cm (0.75 in.).
The free space shall be set based on a 1.3 cm (0.5 in.) ID nozzle, which is
the largest size nozzle used.
The pitot tube must also meet the criteria specified in Method 2
and be calibrated according to the procedure in the calibration section of
that method.
5.1.4 Differential pressure gauge—Inclined manometer capable of
measuring velocity head to within 10% of the minimum measured value. Below
a differential pressure of 1.3 mm (0.05 in.) water gauge, micromanometers
with sensitivities of 0.013 mm (0.0005 in.) should be used. However,
53
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Thermometer
Florisil Tube
Check
Valve
Probe (r^
Reverse-Type
Pitot Tube
Manometer
Control Box
I
Figure A-l. PCB Sampling Train for Incinerators
54
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micromanometers are not easily adaptable to field conditions and are not
easy to use with pulsating flow. Thus, other methods or devices acceptable
to the Administrator may be used when conditions warrant.
5.1.5 Impingers--Four impingers with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases when connected to-
gether as shown in Figure A-l. The first and second impingers are of the
Greenburg-Smith design. The final two impingers are of the Greenburg-Smith
design modified by replacing the tip with a 1.3 cm (1/2 in.) ID glass tube
extending to 1.3 cm (1/2 in.) from the bottom of the flask.
5.1.6 Solid adsorbent tube—Glass with connecting fittings able to
form leak-free, vacuum tight seals without sealant greases (Figure A-2). Ex-
clusive of connectors, the tube has a 2.2 cm inner diameter, is at least 10 cm
long, and has four deep indentations on the inlet end to aid in retaining the
adsorbent. Ground glass caps (or equivalent) must be provided to seal the
adsorbent-filled tube both prior to and following sampling.
5.1.7 Metering system--Vacuum gauge, leak-free pump, thermometers
capable of measuring temperature to within 3°C (~ 5°F), dry gas meter with
27o accuracy at the required sampling rate, and related equipment, or equiv-
alent, as required to maintain an isokinetic sampling rate and to determine
sample volume. When the metering system is used in conjunction with a pitot
tube, the system shall enable checks of isokinetic rates.
5.1.8 Barometer--Mercury, aneroid, or other barometers capable
of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained from a nearby weather bureau
station, in which case the station value shall be requested and an adjust-
ment for elevation differences shall be applied at a rate of -2.5 mm Hg
(0.1 in. Hg) per 30 m (100 ft) elevation increase.
5.2 Sample Recovery
5.2.1 Ground glass caps--To cap off adsorbent tube and the other
sample exposed portions of the train.
5.2.2 Teflon FBI® wash bottle—Two, 500 ml, Nalgene No. 0023A59
or equivalent.
5.2.3 Sample storage containers—Glass bottles, 1 liter, with
TFE®-lined screw caps.
5.2.4 Balance—Triple beam, Ohaus Model 7505 or equivalent.
5.2.5 Aluminum foil—Heavy duty.
55
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^28/12
10cm
-2.5cm O.D.
-2.2cm I.D.
j 28/12
Figure A-2. Florisil Adsorbent Tube
56
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5.2.6 Metal can--To recover used silica gel.
5.3 Analysis
\j 5.3.1 Glass Soxhlet extractors--40 mm ID complete with 45/50 <£
condenser, 24/40 J 250 ml round bottom flask, heating mantle for 250 ml
flask, and power transformer.
5.3.2 Teflon FEP wash bottle--Two, 500 ml, Nalgene No. 0023A59
or equivalent.
5.3.3 Separatory funnel--!,000 ml with TFE® stopcock.
5.3.4 Kuderna-Danish concentrators--500 ml.
5.3.5 Steam bath.
5.3.6 Separatory funnel--50 ml with TFE® stopcock.
5.3.7 Volumetric flask--25.0 ml, glass.
5.3.8 Volumetric flask--5.0 ml, glass.
5.3.9 Culture tubes--13 x 100 mm, glass with TFE®-lined screw caps,
5.3.10 Pipette--5.0 ml glass.
5.3.11 Aluminum block—Drilled to support culture tubes while
heating.
5.3.12 Hot plate--Capable of heating to 200°C.
5.3.13 Teflon®-glass syringe—1 ml, Hamilton 1001 TLL or
equivalent with Teflon® needle.
5.3.14 Syringe--10 ul, Hamilton 701N or equivalent.
5.3.15 Gas chromatograph--Fitted with electron capture detector
capable of operation at 300°C and with 2 mm ID x 1,8 mm glass column packed
with 3% OV-210 on 100/120 mesh inert support (e.g., Supelcoport®).
5.3.16 Electric muffle furnace--Capable of heating to 650°C.
5.3.17 Electric oven—Capable of heating to 150°C.
5.3.18 Disposable glass pipettes with bulbs—To aid transfer of
the extracts.
57
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5.3.19 Porcelain casserole--Capable of withstanding temperatures
as high as 650°C.
6. Reagents
6.1 Sampling
6.1.1 Florisil—Floridin Co., 30/60 mesh, Grade A. The Florisil
is cleaned by 8 hr Soxhlet extraction with hexane and then by drying for
8 hr in an oven at 110°C and is activated by heating to 650°C for 2 hr (not
to exceed 3 hr) in a muffle furnace. After allowing to cool to near 110°C
transfer the clean, active Florisil to a clean, hexane-washed glass jar and
seal with a TFE^1-lined lid. The Florisil should be stored at 110°C until
taken to the field for use. Florisil that has been stored more than 1 month
must be reactivated before use.
6.1.2 Glass wool—Cleaned by thorough rinsing with hexane, dried
in a 110°C oven, and stored in a hexane-washed glass jar with TFE®-lined
screw cap.
6.1.3 Water—Deionized, then glass-distilled, and stored in hexane-
rinsed glass containers with TFE®-lined screw caps.
6.1.4 Silica gel--Indicating type, 6-16 mesh. If previously used,
dry at 175°C for 2 hr. New silica gel may be used as received.
6.1.5 Crushed ice.
6.2 Sample Recovery
6.2.1 Acetone—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.2.2 Hexane—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3 Analysis
6.3.1 Hexane--Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.2 Acetone—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.3.3 Water--Deionized and then glass-distilled, stored in hexane-
rinsed glass containers with TFE®-lined screw caps.
58
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6.3.4 Sodium sulfate (^250*)--Anhydrous, granular. Clean by
overnight Soxhlet extraction with hexane, drying in a 110°C oven, and then
heating to 650°C for 2 hr. Store in 110°C oven or in glass jar closed with
TFE®-lined screw cap.
6.3.5 Sulfuric acid (tUSO/)--Concentrated, ACS reagent grade or
equivalent.
6.3.6 Antimony pentachloride (SbCl,.)--Baker Analyzed Reagent or
equivalent.
6.3.7 Hydrochloric acid (HC1) solution--ACS reagent grade or
equivalent, 50% in water.
6.3.8 Glass wool--Cleaned by thorough rinsing with hexane, dried
in a 110°C oven, and stored in a hexane-rinsed glass jar with TFE®-lined cap.
6.3.9 Decachlorobiphenyl--RFP Corp., No. RPC-60, or equivalent.
6.3.10 Compressed nitrogen--Prepurified.
6.3.11 Carborundum boiling stones--Hengar Co. No. 133-B or equiv-
alent, rinsed with hexane.
7. Procedure
Caution: Section 7.1.1 should be done in the laboratory.
7.1 Sampling. The sampling shall be conducted by competent personnel
experienced with this test procedure and cognizant of the constraints of the
analytical techniques for PCBs, particularly contamination problems.
7.1.1 Pretest preparation. All train components shall be main-
tained and calibrated according to the procedure described in APTD-0576,
unless otherwise specified herein.
7.1.1.1 Cleaning glassware. All glass parts of the train
upstream of and including the adsorbent tube, should be cleaned as described
in Section 3A of the 1974 issue of "Manual of Analytical Methods for Analysis
of Pesticide Residues in Human and Environmental Samples." Special care
should be devoted to the removal of residual silicone grease sealants on
ground glass connections of used glassware. These grease residues should be
removed by soaking several hours in a chromic acid cleaning solution prior
to routine cleaning as described above.
59
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7.1.1.2 Solid adsorbent tube. Weigh 7.5 g of Florisil, ac-
tivated within the last 30 days and still warm from storage in a 110°C oven,
into the adsorbent tube (pre-rinsed with hexane) with a glass wool plug in
the downstream end. Place a second glass wool plug in the tube to hold the
sorbent in the tube. Cap both ends of the tube with ground glasj caps. These
caps should not be removed until the tube is fitted to the train immediately
prior to sampling.
7.1.2 Preliminary determinations. Select the sampling site and
the minimum number of sampling points according to Method 1 or as specified
by the Administrator. Determine the stack pressure, temperature, and the
range of velocity heads using Method 2 and moisture content using Approxi-
mation Method 4 or its alternatives for the purpose of making isokinetic
sampling rate calculations. Estimates may be used. However, final results
will be based on actual measurements made during the test.
Determine the molecular weight of the stack gases using Method 3.
Select a nozzle size based on the maximum velocity head so that
isokinetic sampling can be maintained at a rate less than 0.75 cfm. It is
not necessary to change the nozzle size in order to maintain isokinetic
sampling rates. During the run, do not change the nozzle size.
Select a suitable probe length such that all traverse points can
be sampled. Consider sampling from opposite sides for large stacks to re-
duce the length of probes.
Select a sampling time appropriate for total method sensitivity
and the PCB concentration anticipated. Sampling times should generally fall
within a range of 2 to 4 hr.
It is recommended that a buzzer-timer be incorporated in the con-
trol box (see Figure 1) to alarm the operator to move the probe to the next
sampling point.
In some circumstances, e.g., short batch processes, it may be
necessary to sample through two or more batches to obtain sufficient sample
volume. In these cases, sampling should cease during loading/unloading of
the furnace.
7.1.3 Preparation of collection train. During preparation and
assembly of the sampling train, keep all train openings where contamination
can enter covered until just prior to assembly or until sampling is about to
begin. Immediately prior to assembly, rinse all parts of the train upstream
of the adsorbent tube with hexane.
60
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Mark the probe with heat resistant tape or by some other method at points
indicating the proper distance into the stack or duct for each sampling
point.
Place 200 ml of water in each of the first two impingers, and
leave the third impinger empty. CAUTION: do not use sealant greases in
assembling the train. If the preliminary moisture determination shows that
the stack gases are saturated or supersaturated, one or two additional empty
impingers should be added to the train between the third impinger and the
Florisil tube. See Section 10.1. Place approximately 200 to 300 g or more,
if necessary, of silica gel in the last impinger. Weigh each impinger (stem
included) and record the weights on the impingers and on the data sheet.
Unless otherwise specified by the Administrator, attach a tempera-
ture probe to the metal sheath of the sampling probe so that the sensor is
at least 2.5 cm behind the nozzle and pitot tube and does not touch any
metal.
Assemble the train as shown in Figure A-l. Through all parts of
this method use of sealant greases such as stopcock grease to seal ground
glass joints must be avoided.
Place crushed ice around the impingers.
7.1.4 Leak check procedure--After the sampling train has been as-
sembled, turn on and set (if applicable) the probe heating system(s) to reach
a temperature sufficient to avoid condensation in the probe. Allow time for
the temperature to stabilize. Leak check the train at the sampling site by
plugging the nozzle and pulling a 380 mm Hg (15 in. Hg) vacuum. A leakage
rate in excess of 4% of the average sampling rate of 0.0057 m^/min (0.02 cfm)
whichever is less, is unacceptable.
The following leak check instruction for the sampling train de-
scribed in APTD-0576 and APTD-0581 may be helpful. Start the pump with by-
pass valve fully open and coarse adjust valve completely closed. Partially
open the coarse adjust valve and slowly close the bypass valve until 380 mm
Hg (15 in. Hg) vacuum is reached. Do not reverse direction of bypass valve.
This will cause water to back up into the probe. If 380 mm Hg (15 in. Hg)
is exceeded, either leak check at this higher vacuum or end the leak check
as described below and start over.
When the leak check is completed, first slowly remove the plug
from the inlet to the probe and immediately turn off the vacuum pump. This
prevents the water in the impingers from being forced backward into the
probe.
61
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Leak checks shall be conducted as described above prior to each
test run and at the completion of each test run. If leaks are found to be
in excess of the acceptable rate, the test will be considered invalid. To
reduce lost time due to leakage occurrences, it is recommended that leak
checks be conducted between port changes.
7.1.5 Train operation--During the sampling run, an isokinetic
sampling rate within 107o, or as specified by the Administrator, of true iso-
kinetic shall be maintained. During the run, do not change the nozzle or
any other part of the train in front of and including the Florisil tube.
For each run, record the data required on the data sheets. An
example is shown in Figure A-3. Be sure to record the initial dry gas meter
reading. Record the dry gas meter readings at the beginning and end of each
sampling time increment, when changes in flow rates are made, and when sam-
pling is halted. Take other data point readings at least once at each sam-
ple point during each time increment and additional readings when significant
changes (20% variation in velocity head readings) necessitate additional ad-
justments in flow rate. Be sure to level and zero the manometer.
Clean the portholes prior to the test run to minimize chance of
sampling deposited material. To begin sampling, remove the nozzle cap,
verify (if applicable) that the probe heater is working and up to tempera-
ture, and that the pitot tube and probe are properly positioned. Position
the nozzle at the first traverse point with the tip pointing directly into
the gas stream. Immediately start the pump and adjust the flow to isokinetic
conditions. Nomographs are available for sampling trains using type S pitot
tubes with 0.85 + 0.02 coefficients (C_), and when sampling in air or a stack
gas with equivalent density (molecular weight, M
-------
FIELD DATA
PLANT.
DATE_
PROBE LENGTH AND TYPE.
NOZZLE I.D..
SAMPLING LOCATION.
SAMPLE TYPE
RUN NUMBER
OPERATOR
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE _
STATIC PRESSURE, (P$) _
FILTER NUMBER (s)
ASSUMED MOISTURE. ',
SAMPLE BOX NUMBER.
METER BOX NUMBER _
METER AHg
CFACTOR
PROBE HEATER SETTING.
HEATER BOX SETTING
REFERENCE ap
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY.
MINUTES
TRAVERSE
POINT
NUMBER
NSV CLOCK TIME
™pL1NG^NcSchK>
TIME, mm N^
'
GAS METER READING
-------
During the test run, make periodic adjustments to keep the probe
temperature at the proper value. Add more ice and, if necessary, salt to
the ice bath, to maintain a temperature of less than 20°C (68°F) at the
impinger/silica gel outlet, to avoid excessive moisture losses. Also, peri-
odically check the level and zero of the manometer.
If the pressure drop across the train becomes high enough to make
isokinetic sampling difficult to maintain, the test run should be terminated.
Under no circumstances should the train be disassembled during a test run to
determine and correct causes of excessive pressure drops.
At the end of the sample run, turn off the pump, remove the probe
and nozzle from the stack, and record the final dry gas meter reading. Per-
form a leak check.* Calculate percent isokinetic (see calculation section)
to determine whether another test run should be made. If there is difficulty
in maintaining isokinetic rates due to source conditions, consult with the
Administrator for possible variance on the isokinetic rates.
7.1.6 Blank train—For each series of test runs, set up a blank
train in a manner identical to that described above, but with the nozzle
capped with aluminum foil and the exit end of the last impinger capped with
a ground glass cap. Allow the train to remain assembled for a period equiv-
alent to one test run. Recover the blank sample as described in Section 7.2.
7.2 Sample recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period.
When the probe can be safely handled, wipe off all external par-
ticulate matter near the tip of the probe nozzle. Remove the probe from the
train and close off both ends with aluminum foil. Cap off the inlet to the
train with a ground glass cap.
Transfer the probe and impinger assembly to the cleanup area. This
area should be clean and protected from the wind so that the chances of con-
taminating or losing the sample will be minimized.
Inspect the train prior to and during disassembly and note any ab-
normal conditions. Treat the samples as follows:
7.2.1 Adsorbent tube—Remove the Florisil tube from the train and
cap it off with ground glass caps.
With acceptability of the test run to be based on the same criterion as
in 7.1.4.
64
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7.2.2 Sample container No. I—Remove the first three impingers.
Wipe off the outside of each impinger to remove excessive water and other
debris, weigh (stem included), and record the weight on data sheet. Pour
the contents directly into container No. 1 and seal.
7.2.3 Sample container No. 2--Rinse each of the first three im-
pingers sequentially first with 30 ml acetone and then with 30 ml hexane,
and put the rinses into container No. 2. Quantitatively recover material
deposited in the probe using 100 ml acetone and then 100 ml hexane and add
these rinses to container No. 2 and seal.
7.2.4 Silica gel container--Remove the last impinger, wipe the
outside to remove excessive water and other debris, weigh (stem included),
and record weight on data sheet. Transfer the contents to the used silica
gel can.
7.3 Analysis. The analysis of the PCB samples should be conducted by
chemical personnel experienced in determinations of trace organics utilizing
sophisticated, instrumental techniques. All extract transfers should be
made quantitatively by rinsing the apparatus at least three times with hex-
ane and adding the rinses to the receiving container. A boiling stone should
be used in all evaporative steps to control "bumping."
7.3.1 Extraction
7.3.1.1 Adsorbent tube. Expel the entire contents of the
adsorbent tube directly onto a glass wool plug in the sample holder of a
Soxhlet extractor. Although no extraction thimble is required, a glass
thimble with a coarse-fritted bottom may be used.
Rinse the tube with 5 ml acetone and then with 15 ml hexane
and put these rinses into the extractor. Assemble the extraction apparatus
and extract the adsorbent with 170 ml hexane for at least 4 hr. The ex-
tractor should cycle 10 to 14 times per hour. After allowing the extrac-
tion apparatus to cool to ambient temperature, transfer the extract into a
Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml on a steam bath and
allow the evaporator to cool to ambient temperature before disassembly.
Transfer the extract to a 50-ml separatory funnel and set the funnel aside.
7.3.1.2 Sample container No. 1. Transfer the aqueous sam-
ple to a 1,000-ml separatory funnel. Rinse the container with 20 ml acetone
and then with two 20-ml portions of hexane, adding the rinses to the sep-
aratory funnel.
65
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Extract the sample with three 100 ml portions of hexane,
transferring the sequential extracts to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly. Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil extract. The micro column is prepared
by placing a small plug of glass wool in the bottom of the large portion of
a disposable pipette and then adding anhydrous sodium sulfate until the tube
is about half full.
7.3.1.3 Sample container No. 2. Transfer the organic solu-
tion into a 1,000 ml separatory funnel. Rinse the container with two 20 ml
portions of hexane and add the rinses to the separatory funnel. Wash the
sample with three 100 ml portions of water. Discard the aqueous layer and
transfer the organic layer to a Kuderna-Danish evaporator.
Evaporate the extract to about 5 ml and allow the evaporator
to cool to ambient temperature before disassembly. Filter the extract through
a micro column of anhydrous sodium sulfate into the 50 ml separatory funnel
containing the corresponding Florisil and impinger extracts.
7.3.2 Extract cleanup—Clean the combined extracts (in 50 ml
separatory funnel) by shaking with 5 ml concentrated sulfuric acid. Allow
the acid layer to separate and drain it off.
Transfer the hexane layer to a Kuderna-Danish evaporator and evap-
orate to about 5 ml. Allow the evaporator to cool to ambient temperature
before disassembly.
The extract should be essentially colorless. If it still shows
significant color, additional cleanup may be required before assaying for
PCBs. In this event, further clean the extract by liquid chromatography on
Florisil according to procedures described in Section 5A of the 1974 issue
of "Manual of Analytical Methods for Analysis of Pesticide Residues in Human
and Environmental Samples" Reduce the Florisil eluant to about 10 ml by
Kuderna-Danish evaporation techniques described above.
Transfer the cleaned extract to a 25 ml volumetric flask and di-
lute to volume with hexane. Pipette three 5.0 ml aliquots into culture
tubes for perchlorination. Retain the remaining 10 ml for later verifica-
tion, if required (see Section 10.2).
7.3.3 Extract perchlorination--Evaporate the aliquots in the cul-
ture tubes just to dryness with a gentle stream of dry nitrogen. If the ali-
quots will not evaporate to dryness, refer to Section 10.3 concerning special
cases. Add 0.2 ml antimony pentachloride with a 1 ml glass-TFE® syringe and
66
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seal the tube with a TFE®-lined screw cap. Heat the reaction-m-i-xture_to_1.60°C:.i ' '
for 2 hr by placing the tube in a hole ii^jtn aluminum Jjlock on ^_ho.t_p.late..—. ^
Allow the tube to cool to ambient room temperature before adding
about 2 ml of 50% HC1 in water to destroy residual antimony pentachloride.
This is a convenient "stopping point" in the perchlorination procedure.
Extract the reaction mixture by adding about 1 ml hexane to the
tube, shake, and allow layers to separate. Remove the upper hexane layer
with a disposable pipette and filter through a micro column of anhydrous
sodium sulfate directly into a 5 ml volumetric flask. Repeat the extraction
three times for a total of four extractions. Dilute the extract to volume
with hexane.
7.3.4 PCB determination—Assay the perchlorinated extracts for
decachlorobiphenyl (DCB) by gas chromatographic comparison with DCS stan-
dard solutions and correct this result for the DCB concentration determined
for the blank train. (Column temperature and carrier gas flow parameters
of 240°C and 30 ml/min, are typically appropriate. The concentrations of the
standard solutions should allow fairly close comparison with DCB in the sam-
ple extracts. Standards near 25 to 50 picograms/microliter may be appropriate.)
8. Calibration
Maintain a laboratory log of all calibrations.
8.1 Sampling Train
8.1.1 Probe nozzle--Using a micrometer, measure the inside dia-
meter of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time and obtain the average of
the measurements. The difference between the high and low numbers shall not
exceed 0.1 mm (0.004 in.).
When nozzles become nicked, dented, or corroded, they shall be re-
shaped, sharpened, and recalibrated before use.
Each nozzle shall be permanently and uniquely identified.
8.1.2 Pitot tube—The pitot tube shall be calibrated according
to the procedure outlined in Method 2.
8.1.3 Dry gas meter and orifice meter—Both meters shall be cali-
brated according to the procedure outlined in APTD-0576. When diaphragm
67
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pumps with bypass valves are used, check for proper metering system design
by calibrating the dry gas meter at an additional flow rate of 0.0057 m^/min
(0.2 cfm) with the bypass valve fully opened and then with it fully closed.
If there is more than + 27» difference in flow rates when compared to the fully
closed position of the bypass valve, the system is not designed properly and
must be corrected.
8.1.4 Probe heater calibration--The probe heating system shall be
calibrated according to the procedure contained in APTD-0576. Probes con-
structed according to APTD-0581 need not be calibrated if the calibration
curves in APTD-0576 are used.
8.1.5 Temperature gauges--Calibrate dial and liquid filled bulb
thermometers against mercury-in-glass thermometers. Thermocouples should
be calibrated in constant temperature baths.
8.2 Analytical Apparatus
8.2.1 Gas chromatograph--Prepare a working curve from at least
five standard injections of different volumes of the DCB standard.
9. Calculations
Carry out calculations, retaining at least one extra decimal fig-
ure beyond that of the acquired data. Round off figures after final calcu-
lations.
9.1 Nomenclature
G = Corrected weight of DCB in nth perchlorinated aliquot (n = 1, 2, 3), ug.
G = Total weight of PCBs (as DCB) in sample, ug.
s
C = Concentration of PCBs in stack gas, ug/m , corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry basis.
A = Cross-sectional area of nozzle, nr (ft2).
B = Water vapor in the gas stream, proportion by volume.
I = Percent of isokinetic sampling.
^ = Molecular weight of water, 18 g/g-mole (18 Ib/lb-mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. Hg).
68
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Pg = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in Hg).
R = Ideal gas constant, 0.06236 mm Hg-m3/°K-g-mole (21.83 in.
Hg-ft3/°R-lb-mole).
Tm = Absolute average dry gas meter temperature °K (°R).
Ts = Absolute average stack gas temperature °K (°R).
Tgtd = Standard absolute temperature, 293°K (528°R).
VIG = Total volume of liquid collected in impingers and silica gel, ml.
volume of water collected equals the weight increase in grams
times 1 ml/gram
V = Volume of gas sample as measured by dry gas meter, dcm (dcf).
Vm(std) = Volu"16 of 8as sample measured by the dry gas meter corrected to
standard conditions, dscm (dscf).
V /st(j) = Volume of water vapor in the gas sample corrected to standard
conditions, son (scf).
Vt = Total volume of sample, ml.
V = Stack gas velocity, calculated by EPA Method 2, m/sec (ft/sec).
s
AH = Average pressure differential across the orifice meter, mm
(in. H20).
pw = Density of water, 1 g/ml (0.00220 Ib/ml).
9 = Total Sampling time, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.
69
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9.2 Average dry gas meter temperature and average orifice pressure
drop. See data sheet (Figure A-3).
9.3 Dry gas volume. Correct the sample volume measured by the dry
gas meter to standard conditions [20°C, 760 mm Hg (68°F, 29.92 in. Hg)] by
using Equation A-l).
Vm(std)
= V
m
Tstd
Tm
+ AH
pbar 13.6
Pstd
= K V,
m
+ AH
Pbar 13.6
m
Equation A-l
where K = 0.3855 °K/mm Hg for metric units
= 17.65 °R/in. Hg for English units
9.4 Volume of water vapor
Pw RT
Vw(std) = Vic ~ — = K Vic
MM pstd.
Equation A-2
where K = 0.00134 m /ml for metric units
= 0.0472 ft3/ml for English units
9.5 Moisture content
Vstd)
Vm(std) + Vw(std)
Equation A-3
If the liquid droplets are present in the gas stream assume the stream
to be saturated and use a psychrometric chart to obtain an approximation
of the moisture percentage.
70
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9.6 Concentration
9.6.1 Calculate the total PCB residue (as DCS) in the sample from
the weights of DCB in the perchlorinated aliquots according to Equation A-4.
G = 5(Gl + G2 + 63) Equation A-4
s
9.6.2 Concentration of PCBs (as DCB) in stack gas. Determine the
concentration of PCBs in the stack gas according to Equation A-5.
G0
C = K Equation A-5
Vm(std)
where K = 35.31 ft3/m3
9.7 Isokinetic variation
9.7.1 Calculations from raw data.
_ 100 TsCKVlc+ (W (Pbar) +AH/13.6)]
1 60 9 vs Ps An
Equation A-6
where K = 0.00346 mm Hg-m3/ml-°K for metric units
= 0.00267 in. Hg-ft3/ml-°R for English units
9.7.2 Calculations from intermediate values.
Ts Vm(std) pstd
100
Tstd vs e An PS 60
Ts Vm(std)
PS vs An 6 (1-Bws) Equation A-7
= K
where K = 4.323 for metric units
= 0.0944 for English units
71
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9.8 Acceptable results. The following range sets the limit on accept-
able isokinetic sampling results:
If 90% < I < 110%, the results are acceptable. If the results are
low in comparison to the standards and I is beyond the acceptable range, the
Administrator may option to accept the results.
10. Special Cases
10.1 Sampling moisture saturated or supersaturated stack gases. One
or two additional modified Greenburg-Smith impingers may be added to the
train between the third impinger and the Florisil tube to accommodate addi-
tional water collection when sampling high moisture gases. Throughout the
preparation, operation, and sample recovery from the train, these additional
impingers should be treated exactly like the third impinger.
10.2 PCB verification. It is recommended that an unperchlorinated
aliquot from at least one sample be subjected to GC/MS examination to verify
that PCB isomers are present.
To accomplish this, the unperchlorinated portion of each extract
is first screened by GC with the same chromatographic system used for DCB
determination except for a cooler column temperature, typically 165 to 200 C.
The elution patterns are compared with those of commercial PCB mixtures (in
hexane solution) to determine the most similar mixture.
After determining what PCB isomers are possible present, the sam-
ple is examined byJjC/MS using multijpJl^^ipjn^ele^tiO£j^52^jiu6LS_fo.r_,io.ns .
characteristic of the molecular clusters of the PCBs possibly present.
10.3 Evaporation of extracts for perchlorination. For cases where the
extract will not evaporate to dryness or excessive PCB loss by volatiliza-
tion is suspected, the hexane may be removed by^azeotrophic evaporatio n from
the hexane/chloroform mixture.
Add 3 ml of chloroform to the aliquot in the culture tube. Add
a boiling chip and concentrate by slow boiling in a water bath to 1 ml.
Repeat the chloroform addition and evaporation three times in order to remove
all residual hexane. Then further concentrate (slowly) to a volume of ap-
proximately 0.1 ml. Under no circumstances should the water bath tempera-
ture be permitted to exceed 76 C or the solvent be evaporated to dryness.
The final volume (0.1 ml) may be determined with sufficient accuracy by
comparison of solvent level with another reaction vial containing 0.1 ml
of chloroform. When a volume of 0.1 ml is achieved, cap the reaction vial
immediately and allow to cool. Proceed with the perchlorination as described
in Section 7.3.3.
72
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11. References
Martin, Robert M., "Construction Details of Isokinetic Source
Sampling Equipment," Environmental Protection Agency, Air Pollution Control
Office Publication No. APTD-0581.
1973 Annual Book of ASTM Standards. Part 23, Designation: D 1179-72.
Thompson, J. F., Ed., "Analysis of Pesticide Residues in Human and
Environmental Samples," Environmental Protection Agency, Research Triangle
Park, N.C., 1974.
73
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PART B. CAPACITOR- AND TRANSFORMER-FILLING PLANTS
1. Principle and Applicability
1.1 Principle. Gaseous and particulate PCBs are withdrawn isokinet-
ically from the source. The PCBs are collected on Florisil and determined
by gas chromatography against an Aroclor® standard.
1.2 Applicability. This method is applicable for the determination
of PCB emissions from the room air, room air exhaust and process point ex-
hausts at capacitor- and transformer-filling plants.
2. Range and Sensitivity
The range of the analytical method may be expanded considerably
through concentration and/or dilution of the extract. The total method
sensitivity is also highly dependent on the volume of gases sampled. How-
ever, sensitivity of the total method is near 1 ug per test or near 10 ng
per test where the perchlorination assay method is used.
3. Interferences
Throughout all stages of sample handling and analysis, care should
be taken to avoid contact of samples and extracts with synthetic organic ma-
terials other than TFF;® (polytetraf luoroethylene) . Lubricating and sealing
greases should not be used on the sample exposed portions of the sampling
train.
4. Precision and Accuracy
Sampling with identical and paired sampling trains, the precision
of the method should be 10 to 15% of the PCB concentration measured. Re-
covery efficiencies on source samples spiked with PCB compounds ranged from
85 to 95% of the spike.
5. Apparatus
5.1 Sampling Train. The sampling train, see Figure B-l, consists of a
glass-lined probe, an adsorbent tube containing Florisil, and the appropriate
valving and flow meter controls for isokinetic sampling as described in Part A
of the procedure. The sampling apparatus in Figure B-l is the same as that in
Figure A-l and Section 5.1 of Part A, except that the Smith-Greenburg impingers
and heated probe are not used. If condensation of significant quantities of
moisture prior to the solid adsorbent is expected, Part A of the method should
be used. Since probes and adsorbent tubes are not cleaned up in the field, a
sufficient number must be provided for sampling and allowance for breakage.
74
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Probe (to sample from duct) ^M
Glass- lined Probe
Florisil
Glass Wool
Thermometers
7) (7
Integrated I
Flow Meter I
Check Valve
Air
Tight
Pump
Vacuum
Line
Figure B-l. PCB Sampling Train for Capacitor- and
Transformer-Filling Plants
75
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5.2 Sample Recovery. Heavy duty aluminum foil must be provided to
cap off the probe prior to shipment.
5.3 Analysis. The equipment required for the analysis is identical to
that specified in Part A except that the equipment necessary for perchlorina-
tion of the PCBs collected to the decachlorobiphenyl form is not required.
(Perchlorination of the sample here is optional and should be employed only
if the GC fingerprint technique of this procedure is not applicable.)
6. Reagents
6.1 Sampling
6.1.1 Florisil--Floridin Company, 30/60 mesh, Grade A. The Flori-
sil is cleaned by overnight Soxhlet extraction with hexane and then drying
overnight at 110°C and is activated by heating to 650°C for 2 hr (not to ex-
ceed 3 hr) in a muffle furnace. After allowing to cool to near 110°C, trans-
fer the clean, active Florisil to a clean, hexane-washed glass jar and seal
with a TFF^-lined lid. The Florisil should be stored at 110°C until taken
to the field for use. Florisil that has been stored more than 1 month must
be reactivated.
6.1.2 Glass wool--Cleaned by thorough rinsing with hexane, dried
in a 110°C oven, and stored in a hexane-washed glass jar with TFF^-lined
screw cap.
6.2 Analysis
6.2.1 Hexane—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.2.2 Acetone—Pesticide quality, Burdick and Jackson "Distilled
in Glass" or equivalent, stored in original containers and used as received.
6.2.3 Sodium sulfate (Na2864)--Anhydrous, granular. Clean by
overnight Soxhlet extraction with hexane, drying in a 110°C oven, and then
heating to 650°C for 2 hr. Store in 110°C oven or in glass jar closed with
TFF;®-lined screw cap.
6.2.4 Sulfuric acid (I^SO,)--Concentrated, ACS reagent grade or
equivalent.
6.2.5 Glass wool—Cleaned by thorough rinsing with hexane, dried
in a 110°C oven, and stored in a hexane-rinsed glass jar with TFFP-lined cap.
76
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6.2.6 Carborundum boiling stones--Hengar Company No. 133-B or
equivalent, rinsed with hexane.
6.2.7 Standard Aroclor PCB mixtures--Aroclors® 1016, 1221, 1232,
1242, 1248, 1254, 1260, and 1262 may be obtained from the Pesticide Reposi-
tory, EPA/HERL/ETD, Research Triangle Park, North Carolina.
7. Procedure
7.1 Sampling. The sampling shall be conducted by competent personnel
knowledgeable with this test procedure and cognizant of the constraints of
the analytical techniques for PCBs, particularly contamination problems.
The sampling procedure for capacitor and transformer plants is
identical to that described in Part A with the following exceptions: (a)
'impingers and a heatable probe are not required prior to the adsorbent
tube; and (b) the PCB concentrations may be considerably higher for ca-
pacitor and transformer plants, compared to most incinerators, thus the
sampling time can be less than the 2 hr specified in Part A.
The selection of sampling time and rate should be based on the
approximate levels of PCB residues expected in the sample. The sampling
rate should not exceed 14 liters/min and may typically fall in the range
of 5 to 10 liters/min. Sampling times should be more than 20 min but
should not exceed 4 hr.
Because the processes for filling the capacitors and transformers
can vary significantly between plants, isokinetic sampling is required in
the procedure. However, if it can be shown to the satisfaction of the
Administrator that isokinetic sampling is not necessary, then sampling at
a proportional rate is an acceptable alternative. Proportional or constant
flow rate sampling may also be necessary in cases where the standard pitot/
nozzle assembly physically blocks a significant portion of the stack or
where the flow rate is too low (less than 10 ft/min) for the pitot tube.
7.2 Sample Recovery
7.2.1 Adsorbent tube--Remove the Florisil tube from the collec-
tion system and cap it off with ground glass caps for shipment to the ana-
lytical laboratory.
7.2.2 Probe (where applicable)--Remove the probe from the col-
lection system and cap it off with aluminum foil.
77
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7.3 Analysis. The analysis of the PCB samples should be conducted by
chemical personnel experienced in determinations of trace organics utilizing
sophisticated instrumental techniques. All extract transfers should be made
quantitatively by rinsing the apparatus at least three times with hexane and
adding the rinses to the receiving container. A boiling stone should be used
in all evaporative steps to control "bumping."
7.3.1 Extraction
7.3.1.1 Adsorbent tube. Expel the entire contents of the
adsorbent tube directly onto a glass wool plug in the sample holder of a
Soxhlet extractor. Although no extraction thimble is required, a glass
thimble with a coarse-fritted bottom may be used.
Rinse the tube with about 5 ml acetone and then about 15 ml
hexane into the extractor. Assemble the extraction apparatus and extract
the adsorbent with 170 ml hexane for at least 4 hr. The extractor should
cycle 10 to 14 times per hour. After allowing the extraction apparatus to
cool to ambient temperature, transfer the extract into a Kuderna-Danish
evaporator.
Evaporate the extract on a steam bath to about 5 ml and al-
low the evaporator to cool to ambient temperature before disassembly. Trans-
fer the extract to a 50 ml separately funnel and set the funnel aside.
7.3.1.2 Probe (where applicable). Rinse the probe with hex-
ane into a Kuderna-Danish evaporator. Evaporate the extract to about 5 ml
and allow the evaporator to cool to ambient temperature before disassembly.
Add the concentrated extract to the 50-ml separately funnel containing the
corresponding Florisil extract.
7.3.2 Extract cleanup—Clean the combined extracts (in 50-ml
separatory funnel) by shaking with 5 ml concentrated sulfuric acid. Allow
the acid layer to separate and drain it off.
Transfer the hexane layer to a Kuderna-Danish evaporator and evap-
orate to about 5 ml. Allow the evaporator to cool to ambient temperature
before disassembly.
The extract should be essentially colorless. If it still shows
significant color, additional cleanup may be required before assaying for
PCBs. In this event, further clean the extract by liquid chromatography on
Florisil according to procedures described in Section 5A of the 1974 issue
of "Manual of Analytical Methods for Analysis of Pesticide Residues in Human
and Environmental Samples." Reduce the Florisil eluant to about 10 ml by
Kuderna-Danish evaporation techniques described above.
78
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Transfer the cleaned extract to a 25-ml volumetric flask and dilute
to volume with hexane for gas chromatographic analysis.
7.3.3 PCB determination—Assay the cleaned extracts by gas chromato-
graphic comparison with standard solutions of a similar commercial PCB mixture
(A column temperature between 165 and 200°C at a flow rate of 30 ml/min may be
appropriate. Aroclor® standard solutions at concentrations near 10 ng/ul should
be appropriate for calibration of the gas chromatograph.) If PCB mixtures were
being used at the sampling site, a standard solution of that mixture, e.g.,
Aroclor® 1016, will likely be appropriate. Quantitation should be based on the
summed areas of at least five major peaks coincident in the chromatograms of
the sample extracts and standards. The range and sensitivity of the method
may be extended somewhat by diluting concentrated extracts with hexane or
concentrating dilute extracts by evaporation under a gentle stream of dry
nitrogen. If the sample chromatograms do not closely resemble a particular
PCB standard, e.g., in the case of emissions from more than one Aroclor®
product, refer to Section 10.1 concerning Special Cases. Correct the PCB
assays for PCBs determined in the blank train.
8. Calibration
Maintain a laboratory log of all calibrations.
8.1 Sampling Train
8.1.1 Probe nozzle—Using a micrometer, measure the inside diameter
of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate mea-
surements using different diameters each time and obtain the average of the
measurements. The difference between the high and low numbers shall not ex-
ceed 0.1 mm (0.004 in.).
When nozzles become nicked, dented, or corroded, they shall be re-
shaped, sharpened, and recalibrated before use.
Each nozzle shall be permanently and uniquely identified.
8.1.2 Pitot tube—The pitot tube shall be calibrated according
to the procedure outlined in Method 2.
8.1.3 Dry gas meter and orifice meter—Both meters shall be cali-
brated according to the procedure outlined in APTD-0576. When diaphragm
pumps with bypass valves are used, check for proper metering system design
by calibrating the dry gas meter at an additional flow rate of 0.0057 m3/min
(0.2 cfm) with the bypass valve fully opened and then with it fully closed.
If there is more than + 2% difference in flow rates when compared to the
fully closed position of the bypass valve, the system is not designed properly
and must be corrected.
79
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8.1.4 Temperature gauges--Calibrate dial and liquid filled bulb
thermometers against mercury-in-glass thermometers. Thermocouples need not
be calibrated. For other devices, check with the Administrator.
8.2 Analytical Apparatus
8.2.1 Gas chromatograph--Prepare a working curve from at least
five standard injections of different volumes of the Aroclor® standard in
hexane solution.
9. Calculations
Carry out calculations, retaining at least one extra decimal fig-
ure beyond that of the acquired data. Round off figures after final calcu-
lations.
9.1 Nomenclature
Gs = Total weight of Aroclor® in sample, ug.
GS = Concentration of Aroclor® in stack gas, ug/m3, corrected to
standard conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) .
An = Cross-sectional area of nozzle, m^ (ft2).
I = Percent of isokinetic sampling.
**bar = Barometric pressure at the sampling site, mm Hg (in. Hg) .
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
pstd = standard absolute pressure, 760 mm Hg (29.92 in Hg).
R = Ideal gas constant, 0.06236 mm Hg-m3/°K-g-mole (21.83 in.
Hg-ft3/°R-lb-mole).
Tm = Absolute average dry gas meter temperature °K (°R).
Ts = Absolute average stack gas temperature °K (°R).
Tstd = Standard absolute temperature, 293°K (528°R).
Vm = Volume of gas sample as measured by dry gas meter, dcm (dcf).
80
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Vm(std) = Volume of gas sample measured by the dry gas meter corrected to
standard conditions, dscm (dscf).
Vs = Stack gas velocity, calculated by Method 2, Equation 2 to 7, m/sec
(ft/sec).
AH - Average pressure differential across the orifice meter, mm H20
(in. H20).
6 = Total sampling time, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.
9.2 Average dry gas meter temperature and average orifice pressure
drop.
9.3 Dry Gas Volume. Correct the sample volume measured by the dry
gas meter to standard conditions [20°C, 760 mm Hg (68°F, 29.92 in. Hg)]
by using Equation B-l.
Tstd
AH
Pbar +13.6
AH
= KVm pbar +13.6
vm(std) = vm
xm ^std Am
Equation B-l
where K = 0.3855 °K/mm Hg for metric units
= 17.65 °R/in. Hg for English units
9.4 Concentration
9.4.1 Concentration of Aroclor® in stack gas. Determine the
concentration of Aroclor® in the stack gas according to Equation B-2.
Cs = s Equation B-2
vm(std)
81
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10. Special Cases
10.1 Quantitation of PCS Residues Not Similar to a Commercial Mixture.
In cases where the composition of the PCB residue does not closely resemble
an available commercial PCB mixture, i.e., from comparison of EC-GC chromato-
grams, direct quantitation against available standard mixtures may be diffi-
cult and inaccurate. These extracts should be split, perchlorinated, and
total PCBs quantitated by procedures described in Part A, Sections 7.3.2,
7.3.3, and 7.3.4, and the total PCB residue of the sample calculated from
Equation A-4.
10.2 PCB Verification. It is recommended that an unperchlorinated
aliquot from at least one sample be subjected to GC/MS examination to ver-
ify that PCB isomers are present.
After determining what PCB isomers are possibly present by the
quantitation procedures in Section 7.3.3, the sample is examined by GC/MS
using multiple ion selection techniques for ions characteristic of the
molecular clusters of the PCBs possibly present.
11. Reference
Martin, Robert M., "Construction Details of Isokinetic Source
Sampling Equipment," Environmental Protection Agency, Air Pollution Control
Office of Publication No. APTD-0581.
1973 Annual Book of ASTM Standards, Part 23, Designation: D 1179-72
Thompson, J. F., Ed., "Analysis of Pesticide Residues in Human and
Environmental Samples," Environmental Protection Agency, Research Triangle
Park, N.C., 1974.
82
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
i. REPORT NO.
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Methods for Determining the Polychlorinated Biphenyl
Emissions from Incineration and Capacitor and
Transformer Filling Plants
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Clarence L.
8. PERFORMING ORGANIZATION REPORT NO.
Haile and Emile Baladi
9. PERFORMING'ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Blvd.
Kansas City, MO 64110
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-1780
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Environmental Monitoring and Support Laboratory
Office of Res-earch and Development
U.S. Environmental Protection Agency
Final Report
14. SPONSORING AGENCY CODE
Poc;
iangl
=IY NOT
g Park, North Carolina 27711
EPA-ORD
15. SUPPLEMENTARY
TES
16. ABSTRACT
Described are methods to measure the polychlorinated biphenyl (PCB) emissions
from the stacks of municipal waste, industrial waste, and sewage sludge incinerators
and from capacitor and transformer filling plants. The PCB emissions from the
incineration plants are collected by impingement in water and adsorption on Florisil,
The samples are extracted with hexane, concentrated through evaporation of the sol-
vent, perchlorinated, and the polychlorinated biphenyl content measured as the
decachlorinated isomer using a gas chromatograph equipped with a flame ionization
detector. The PCB emissions from the capacitor and transformer filling plants are
collected directly on Florisil, extracted with hexane and quantified against the
appropriate Aroclor using a gas chromatograph.
The methods were developed from laboratory studies and field tested at nine .
incineration plants and two transformer filling plants.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Municipal Incinerators, Industrial Incin-
erators, Sewage Sludge Incinerators,
Capacitor Filling Plants, Transformer
Filling Plants, Polychlorinated Biphenyls,
Measuring
Methods Evaluation
Methods Development
Stationary Sources
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
90
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
83
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