Environmental Protection Technology Series
UTILITY OF SOLID SORBENTS FOR
SAMPLING ORGANIC EMISSIONS FROM
STATIONARY SOURCES
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U. S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-76-201
July 1976
UTILITY OF SOLID SORBENTS
FOR SAMPLING ORGANIC EMISSIONS
FROM STATIONARY SOURCES
by
Arthur D. Snyder, F. Neil Hodgson,
M.A. Kemmer, and J.R. McKendree
Monsanto Research Corporation
P. O. Box 8 (Station B)
Dayton, OH 45407
Contract No. 68-02-1411, Task 10
ROAPNo. 21ACX-094
Program Element No. 1AB013
EPA Project Officer: L.D.Johnson
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
This report presents the results of a study designed to
assess the utility of porous polymer adsorbents as a means
for sampling and concentrating trace organic emissions from
stationary sources. Emissions were sampled from two indus-
trial field sites employing Tedlar bags. The bags, in turn,
were sampled employing small porous polymer sampling tubes
backed up by a cryogenic thermal-gradient sampling system
to assess the efficiencies of adsorption of the trace organic
species. In addition to the experimental results, conclu-
sions and recommendations, a detailed statement of the prob-
lem of sampling trace organics in industrial emissions is
presented in the Appendices. This later discussion includes
a presentation of (1) the characteristics of stationary
sources emitting organic species; (2) an assessment of
present sampling techniques for trace organic emissions;
(3) a review of the use of porous polymer adsorbents in
sampling; and (4) the characteristics of porous polymer
sorbents and their potential limiting properties.
It is concluded that the use of porous polymer adsorption
tubes can serve as a convenient means for concentrating a
range of higher boiling (B.P. >120°C) trace organic emis-
sions in a highly portable field sampling unit which is
readily interfaced with gas-chromatographic or tandem-coupled
GC/mass-spectrometric instrumentation for thermal desorption
and subsequent quantitation in the laboratory. Alternatively,
the porous polymer tubes can be extracted with liquid sol-
vents for subsequent analysis.
ii
-------
TABLE OF CONTENTS
Page
ABSTRACT ii
LIST OP FIGURES iv
LIST OF TABLES v
ACKNOWLEDGMENTS vl
SECTIONS
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Experimental Approach 7
V Sampling and Analysis Techniques 9
VI Experimental Results -^
VII Analysis of Data and Discussion 2°
VIII References 30
APPENDICES
A. Characteristics of Stationary Sources Emitting 32
Organic Species
B. Assessment of Present Sampling Techniques 42
C. Use of Porous Polymer Adsorbents in Sampling 46
D. Characteristics of Porour Polymer sorbents and 50
Potential Limiting Properties
E. References Cited in Appendices 69
ill
-------
FIGURES
No. Page
1 Porous Polymer Sampling Train 10
2 Thermal-gradient Tube Design 12
iv
-------
TABLES
No. Page
1 Combinations of Porous Polymer and Thermal- 16
Gradient Tube Packings Employed for Plant A
Sampling
2 Sampling Data - Plant A 17
3 Analysis Results - Plant A Collector Tubes 19
4 Response of FID to Various Compounds 20
5 Combinations of Porous Polymer and Thermal- 21
Gradient Tube Packings Employed for Plant B
Sampling
6 Sampling Data - Plant B 22
7 Analysis Results - Plant B Collector Tubes 25
8 Statistical Analysis of Total Collection by 27
Pairs - Plant A
9 Statistical Analysis of Total Collection by 28
Pairs - Plant B
v
-------
ACKNOWLEDGMENTS
The support of the following Dayton Laboratory - Monsanto
Research Corporation personnel is gratefully acknowledged
Mr. J.V. Pustinger for preparation of a portion of the
Appendices; Mr. H.R. DuFour for assistance in design and
fabrication of the cryogenic thermal-gradient tubes; and
Mr. N.F. May for conducting the sampling effort reported.
vi
-------
SECTION I
CONCLUSIONS
The objective of this study was to investigate the utility
of solid adsorbents, and specifically porous polymers, as
media for sampling organic emissions from stationary sources.
While the limited quantity of data collected during the study
does not permit a definitive statement as to the utility of
porous polymers as sampling media, the results demonstrate
that with knowledgeable use, porous polymer adsorption tubes
represent a convenient, highly portable means for semi-
quantitative and even quantitative sampling of stationary
sources characterized by a wide range of trace organic
emissions. The degree of success in employing porous polymer
media to concentrate trace organic species in emissions is
dependent upon the proper selection of the porous polymer(s)
to be employed in a given sampling program. For best results,
this selection must be based upon a knowledge of both the
polymer media physical and chemical properties and the
emission characteristics of the source.
One drawback in the use of porous polymer adsorbent media
for sampling of trace organic emissions is their inability
to efficiently retain low molecular weight or highly volatile
species such as C, to C_ hydrocarbons, ethers etc., when
sampling at ambient temperatures. These lighter organic
species must be sampled by other means (e.g., cryogenic
trapping) in order to be quantitated.
-------
In the use of porous polymer media, care must be taken to
assure that the total capacity of the porous polymer adsor-
bents are not exceeded in field sampling. Some knowledge of
the level of total organics from the source and the retention
capacity of the polymers is required to assure that break-
through does not occur due to sampling of excessive total
volumes of emissions. Equally important is the control of
sampling volume flow rate since excessive sampling rates can
lead to inefficient adsorption.
When the above precautions are observed, the use of small
porous polymer adsorption tubes can serve as a convenient
means for concentrating a range of trace organic emissions
in a highly portable field sampling unit which is readily
interfaced in the laboratory with gas-chromotographic and
on tandem-coupled GC/mass-spectrometric instrumentation for
quantitation of emissions.
Based on the above, it should be stated that porous polymer
adsorption tubes do not represent a panacea for solution of
all trace organic emissions sampling problems. Each of the
polymers possess characteristic adsorption properties that
can be tailored to a given source emission sampling problem
depending upon the anticipated composition of the trace or-
ganic emissions. A generalized sampling procedure employing
ambient-temperature porous polymer sampling tubes is not
feasible due to inefficiencies in adsorbing low boiling
trace organic materials. In cases where the concern is
primarily with higher boiling species (>120°C), the sampling
procedure employing Tenax GC as a sorbent should represent
a convenient and accurate solution to this problem.
-------
SECTION II
RECOMMENDATIONS
The successful application of porous polymers as adsorption
media for sampling of trace organic emissions requires proper
selection of the solid substrate and a matching of its
chemical and physical properties with that of the source
emissions. The following laboratory and field experimental
approaches can assist in assuring an acceptable data quality
in field sampling efforts using porous polymers.
•Laboratory testing of porous polymer adsorption capa-
cities should be conducted employing a dynamic system
for generation of known standards of trace organics
in air.
•When there is no pre-knowledge of the emissions levels
of total organics at a given field site either one of
two approaches can be employed to assure that break-
through of the polymer media will not occur: (1) a
field measurement of the total hydrocarbon concentra-
tion by flame ionization detection, along with an esti-
mated average molecular weight of organic emissions, will
serve to estimate appropriate sampling times, or (2)
several porous polymer tubes can be employed to sample
over different time lengths (e.g., 5, 10, 15 min.), with
subsequent laboratory analysis permitting a decision
as to the optimum sampling time for reporting purposes.
-------
•The coupling of two or more porous polymer sampling
tubes in series will often yield excellent results.
An example of this approach would be the use of Tenax
GC followed by Chromosorb 102 or Porapak Q. In this
case the Tenax GC demonstrates a high efficiency for
adsorption of trace organic species above 6 carbons
in chain length. The lower molecular weight organics
would be adsorbed more efficiently in the second ad-
sorption tube.
An alternative sampling method for low boiling trace organic
emissions is suggested based on the use of the thermal-gradient
sampling tube used in this study. Two major drawbacks in
use of this system in its present state of refinement are
(1) in sampling of emissions high in water vapor content a
means for condensation of water before the cryogenic trap
must be devised, and (2) the present system of delivering
liquid-nitrogen-cooled nitrogen to the thermal-gradient tube
is excessively cumbersome in weight and size for field
sampling operations. It is recommended that a study be
conducted to redesign the existing thermalgradient approach
into a more portable system and to evaluate its performance
as a potentially attractive general method for sampling of
both low- and high-boiling trace organic emissions In the
field.
-------
SECTION III
INTRODUCTION
A pressing need exists for a general method for sampling
organic emissions from stationary sources for purposes of
source assessment or source inventory of manufacturing
plants which produce organic chemicals or employ them in
manufacture of other products. These sources are frequently
characterized as emitting a large number of individual organic
species of varying potential health hazard. The alternative
to development of a general method is the development of
specific approaches for each emission component where ex-
treme care must be taken to assure that interferences from
structurally similar emissions do not occur. This alterna-
tive is impractical from both a technical and an economic
viewpoint.
The objective of this task study was to investigate the
utility of solid sorbents, and specifically porous polymer
beads, as media for sampling organic emissions from station-
ary sources. While sampling tubes containing porous polymers
have been employed in the sampling of trace organics in
ambient air, limited systematic studies of the various poly-
mers have been conducted for ambient air applications, and
only limited experience has been gained in the use of porous
polymer bead adsorbents for sampling of industrial stationary
source emissions.
A more complete understanding of the scope of the problem of
developing a general sampling method for organic emissions
will be obtained by reading the material contained in the
-------
Appendices to this report. Appendix A summarizes the charac-
teristics of stationary sources emitting organic species in
a unit process format. This listing includes composition,
humidity, acid content, temperature, pressure, and flow rate,
Also included are listings of organic species identified as
pollutants and a listing of industrial sources of organic
emissions. Appendix B presents an assessment of techniques
that are commonly employed for sampling of organic emissions,
Appendix C presents a historical review of the use of porous
polymers in sampling while Appendix D discusses the charac-
teristics of these materials and their potential limiting
properties as adsorbent media for concentration of trace
organic emissions.
-------
SECTION IV
EXPERIMENTAL APPROACH
The purpose of this task study was to investigate the utility
of solid sorbents for sampling organic emissions from sta-
tionary industrial sources. This information was required
for development of general sampling and analysis procedures
for assessing emissions from industrial sources which produce
organic chemicals or employ them in manufacture of products.
The long-range objective of the study was to develop infor-
mation which might lead to the design of a portable sampling
technique for trace organic emissions that would require
minimal support equipment and would be readily interfaced
with laboratory analytical systems.
The utility of porous polymer bead materials as adsorbent
media for concentrating organic emissions was studied employ-
ing actual gaseous emissions from two industrial stationary
sources. While controlled laboratory studies of adsorption/
desorption efficiency and break-through or capacity measure-
ments on porous polymers would be of interest, few industrial
emission sources can be simulated accurately in a laboratory
evaluation. The use of actual process emissions was con-
sidered to be a more realistic and practical approach to
evaluation of the porous polymer media.
The original intent in the study was to sample source emis-
sions under field conditions in the process of scheduled
sampling efforts under the Source Assessment Program (EPA
68-02-1874). When difficulties were encountered in obtaining
plant cooperation for this effort, the approach was altered.
-------
Samples were collected in the field employing Tedlar bags
which were subsequently sampled in the laboratory under
ambient temperature conditions. This latter approach re-
sulted in sampling of only the more volatile organic species
which did not condense on the surface of the bag and limited
the concentration of water vapor to its partial pressure at
room temperature. The conditions under which the porous
polymer media were tested were therefore significantly less
adverse than originally planned since source characteristics
of high temperature and high humidity were not simulated.
Since the composition of the organics in the Tedlar bags was
unknown, an independent measure of the true value for organic
emissions was required in order to assess the efficiencies of
the porous polymers as adsorbent media. This was accom-
plished by backing up the porous polymer tubes with a
cryogenically-cooled thermal-gradient tube patterned after
that described by R. E. Kaiser (Ref. 1). The thermal-gradient
tube was employed to isolate organic emissions that eluted
from the primary sampling tube.
The performances of the porous polymer tubes were quantitated
by subsequent laboratory analysis of the collection tubes
and the thermal-gradient tubes employing gas chromatographic
and tandem-coupled GC/mass spectrometric techniques.
-------
SECTION V
SAMPLING AND ANALYSIS TECHNIQUES
A. SAMPLING TRAIN
The sampling train employed in the porous polymer performance
tests is shown schematically in Figure 1. An evacuated
cylinder was used as a sampling gas driving force. The valve
and rotometer upstream of the tank was used to adjust flow
rate in the general region of 150 cc/minute. Sampling was
conducted over a 20-minute period for a total sampled volume
of about 3 liters of gas. The cryogenic thermal-gradient
tubes fitted with thermocouples and the porous polymer adsorp-
tion tubes are constructed of stainless steel and standard
Swagelok fittings.
Some details of the sampling system are included as follows:
-The evacuated cylinder was a 0.42 cu.ft. Freon tank
fitted with a thermometer and a 3-in. vacuum gauge to
permit calculation of total volume sampled.
-The liquid nitrogen dewar was a four-liter Nalgene
dewar flask (Cat. #4150) constructed of double-walled
highly crosslinked polyethylene.
-The porous polymer tube is a 7-inch length of 1/4-in.
304 stainless steel tube fitted with Swagelok fittings
and plugs.
-------
/THERMOCOUPLES
TEMPERATURE GAUGE
PRESSURE GAUGE
V
c=^
V,
VACUUM PUMP
HEATED SECTION
POLYMER PACKED TUBE
STAINLESS STEEL PROBE CONDENSER
EVACUATED CYCLINDER
LIQUIONITROGENDEWAR
COMPRESSED NITROGEN
Figure 1. Porous polymer sampling train
-------
A photograph of the thermal-gradient tube is shown in
Figure 2. The inner tube of the concentric heat exchanger is
a 20 cm length of 304 SS tube (0.180 in. OD; 0.149 in. ID;
0.015 wall). The outer tube is a 9 cm length of 5/16 in. OD
by 0.020 wall 304 stainless steel tubing. These dimensions
were selected based on the recommendations of R. E. Kaiser
(Ref. 1). The thermocouples are type K (1/16 in. x 6 in.
probe length, Thermoelectric #SK 1110L). The thermocouple
tip penetrates to an area of the inner tube at the center of
the 3/8 in. stainless steel Swagelok tee nitrogen entrance
(and exit). The inner tube is filled with a solid absorbent.
One-quarter inch Swagelok tees serve as the sample gas inlet
and outlet. Above and beyond the cost of stainless fittings
and thermocouples, approximately $40 per Kaiser trap was
required for welding the inner/outer tube and for assembly.
1. Operation of Sampling Train
To prepare for a sampling run, the train was assembled and
leak checked via vacuo with the valve after the sampling
probe closed. The flow of nitroben through the jacketed
thermogradient tube is adjusted so that the entering nitro-
gen flow is near liquid nitrogen temperature. In earlier
work, Kaiser (Ref. 1) employed nitrogen flow rates of from
1200 liter/hour to 2000 liter/hour to maintain the lowest
temperature of the gradient tube at about l60°C. Under his
conditions, about 200 grams of liquid nitrogen was consumed
in a 20 minute sampling period. An initial setting on the
rotometer of 50 ftVhr (ca. 1500 £/hr is recommended. After
thermal equilibrium has been attained (e.g., TC2 and TCU
register about l60°C), the sample run is initiated by
closing Vjj and opening V^ and V^. V~ should be adjusted to
a flow of about 150 cc/minute (0.3 cfm). The nitrogen flow
rate is quickly adjusted so that TC~ registers -l60°C.
Under these conditions TC2 will register about -100°C when
11
-------
c
Figure 2. Thermal-Gradient Tube Design.
12
-------
a 2-ft, .lY'll-in.- heated "U"-tube is upstream of the thermal-
gradient tub'e. After the 20-mihute run, V is .closed, the
temperature and pressure of the tank is noted and the porous
polymer tube and the cryogenic thermalgradient tube are
disconnected, sealed with Swagelok caps and stored in a dry-
ice chest. Normal precautions should be taken so that
liquid nitrogen does not come in contact with the skin.
B. LABORATORY ANALYSIS
The contents of collectors and thermalgradient tubes were
analyzed using a GC/MS system consisting of a CEC 21-104
mass spectrometer with an Infotronics digital readout system
coupled to an F&M Model 700 gas chromatograph. The chromato-
graph was modified by the addition of an F&M 1609 flame
ionization detector and the injection port was altered to
directly accept either the 0.25 in. diameter collectors or
Kaiser tubes. Collectors were desorbed by heating in a
small tube furnace (E. H. Sargent Co.), the temperature of
which was controlled by means of an F&M Scientific Corp.
power proportioning temperature programmer/controller. This
latter unit was also used to control the temperature output
of a laboratory heat gun (Masters Appliance Corp.) which was
used in desorbing the thermal-gradient tubes. A flow of
hot air from the heat gun was directed through the outer
jacket of the tube from the inlet end. The inlet thermo-
couple was used as the sensing couple for the temperature
controller.
Collectors containing Tenax GC or polyimide packings were
desorbed at 220°C, while those containing Porapak or Chromo-
sorb 100 series packings were desorbed at l80°C. Compounds
were flushed from the collectors into the chromatograph by
a flow of helium in a direction opposite of that used in
13
-------
sampling. A splitter located before the FID detector was
used to direct a portion of the effluent to the mass spec-
trometer.
A 7.5-ft x 0.25-in. stainless steel column packed with
Tenax GC was used as an analytical column.
-------
SECTION VI
EXPERIMENTAL RESULTS
Emissions from two plants (A and B) were collected in Tedlar
bags and returned to the Laboratory for sampling.
A. PLANT A RESULTS
Table 1 presents the combinations of porous polymer tube
packings and the solid adsorbent employed in the thermal
gradient tube for Plant A samples. Tenax GC and Dexsil 300
on Chromosorb W (AW, HMDS) were employed as the thermal
gradient tube packing while Chromosorb 102, Chromosorb 103,
Porapak Q, Tenax GC, and an experimental polyimide were the
porous polymers under study. The sampling data for Plant A
emissions are presented in Table 2. The equation employed
for calculation of sample volume is:
Vs = 17.71
where: V = Sample volume at 70°F and 29-92-in. Hg
s
V = Cylinder volume, cu.ft.
c
P = Barometric pressure-cylinder pressure, in. Hg
T = Temperature, °F +460
i,f = initial and final conditions
Analysis of the collector tubes was performed as presented
in Section V.
15
-------
Table 1. COMBINATIONS OP POROUS POLYMER AND
THERMAL GRADIENT TUBE PACKINGS EMPLOYED
FOR PLANT A SAMPLING
Porous Polymer
Chromosorb 102
Chromosorb 103
Porapak Q
Tenax GC
Polyimide^
Thermal Gradient Tube Packing
Tenax GC
X
XX
X
X
-
Dexil 300
X
-
X
X
XX
a
-Polyimide - Crushed polyimide foam - Monsanto
Research Corporation experimental sample.
16
-------
Table 2. SAMPLING DATA - PLANT A
Porous Polymer
Chromosorb 102
Tenax GC
Chromosorb 103
Poropak Q
Polyimide
Chromosorb 103
Chromosorb 102
Tenax GC
Polyimide
Porapak Q
Thermal
Gradient
Dexil 300
Tenax GC
Tenax GC
Dexil 300
Dexil 300
Tenax GC
Tenax GC
Dexil 300
Dexil 300
Tenax GC
Cylinder Pressure
in. Hg, Vacuum
Initial
27.8
28.1
28.8
27-5
25.5
28.5
28.5
27-5
27.0
28.4
Final
19-5
19-9
20.6
19-3
20.3
20.3
20.3
19.4
18.8
20.2
Temperature, °P
Initial
69
73
73
73
70
69
69
74
75
75
Final
72
75
75
74.5
72
71
73
75
76
76
Sampling
Time,
sec .
1775
1165
1083
1215
1085
1156
1276
970
1325
1026
Sample
Volume,
SCF2
0.116
0.114
0.114
0.114
0.115
0.115
0.115
0.114
0.114
0.114
a
-SCF at 70°F and 29-92 in. Hg.
Sampling Conditions:
Nitrogen Flow = 50 cfh
Cylinder Volume = 0.421 cu.ft.
Barometric Pressure = 29-52 in. Hg first 4 runs
29.28 in. Hg last 6 runs
-------
The chromatographic column used in analysis was temperature
programmed from 30°C to 300°C at 10°C/min. Low molecular
weight hydrocarbons of the same carbon number were insuffi-
ciently separated to allow measurement of the mass of each
specie. However, the spectral data in each case indicates
that the alkene is by far the more predominant component.
Weights of components in micrograms are given in Table 3-
Calculated molar responses (Ref. 2) served as a basis for
these calculations and are given in Table 4. These are in
excellent agreement with reported values for these com-
pounds (Ref. 3). To aid in calculating weights of the
various components, molar response factors were converted
to weight responses, also given in Table 4. In cases where
hydrocarbons were unresolved, an average response value was
used. (Responses are very similar and either value could
actually have been used.)
An instrument response factor was established for n-heptane,
This allowed the absolute instrument response to any of the
components to be determined. All calculations are based on
integrated peak areas.
B. PLANT B RESULTS
Table 5 presents the combinations of porous polymer tube
packings and solid adsorbents employed in the thermal
gradient tubes for Plant B samples. The sampling data for
Plant B emissions are presented in Table 6.
The procedure for desorption and analysis of the collector
tubes was identical to that employed for Plant A samples.
The chromatograms obtained for collector tube components
18
-------
Table 3. ANALYSIS RESULTS - PLANT A COLLECTOR TUBES
Collector Pairs (Ambient
Temperature Collector/
Thermal Gradient Tube)
Chromosorb 102/
Dexil 300
Chromosorb 102/
Tenax GC
Porapak Q/
Dexil 300
Porapak Q/
Tenax GC
Tenax GC/
Dexil 300
Tenax GC/
Tenax GC
Chromosorb 103/
Tenax GC
Chromosorb 103/
Tenax GC
Polyimide/
Dexil 300
Polyimide/
Dexil 300
Micrograms Collected «
Ethane/
Ethylene
0.07
0.4
0.09
b
1.0
- o
1.4
0.3
_
0.2
0.008
0.6
0.3
0.9
0.1
0.002
~~
Propane/
Propylene
14
60
15
24.3
33
4.9
22
33
35
0.2
0.4
0.02
19
46
0.8
49
2.8
0.08
1.4
2.4
Acetal-
dehyde
1.2
0.8
1.3
0.2
2.9
1.2
2.0
0.01
-
2.3
1.8
0.4
0.004
0.1
0.3
Butane/
Butene
6.0
0.2
5-3
1.8
6.1
0.1
9.6
0.9
10
0.7
—
10
1.1
1.0
0.7
0.2
0.04
0.08
0.4
Acrylo-
nitrile
0.4
0.4
0.09
_
0.4
0.09
0.3
_
0.4
0.1
0.7
0.03
0.08
0.1
Methacrylo-
nitrile
0.01
0.5
0.1
1.0
0.2
0.2
0.4
—
0.7
0.08
°11~
0.23
0.7
Benzene
6.7
6.0
0.2
—
7.6
0.04
5.1
—
5.8
0.5
0.03
0.2
0.02
1.2
H
VD
^Normalized for 0.114 SCF sample.
-Not analyzed.
-Not detected.
-------
Table
RESPONSE OF FID TO VARIOUS COMPOUNDS
Compound
Ethane
Ethylene
Propane
Propylene
Acetaldehyde
Butane
Butene
Acrylonltrile
Methacryonitrile
Benzene
Heptane
a
Relative
Molar
Response
191
186
293
288
96
394
389
210
305
600
700
Relative
Weight
Response
6.37
6.64
6.66
6.86
2.18
6.79
6.95
3.96
4.55
7-69
7.00
a
-Relative to 700 for heptane
20
-------
Table 5- COMBINATIONS OP POROUS POLYMER AND
THERMAL GRADIENT TUBE PACKINGS EMPLOYED
FOR PLANT B SAMPLING
Porous Polymer
Chromosorb 102
Chromosorb 103
Porapak Q
Tenax GC
Polyimide^
Thermal Gradient Tube Packing
Tenax GC
X
X
X
X
-
Dexil 300
X
X
X
X
X
a
-Polyimide - Crushed polyimide foam - Monsanto
Research Corporation experimental sample.
21
-------
Table 6. SAMPLING DATA - PLANT B
Porous Polymer
Chromosorb 102
Tenax GC
Chromosorb 103
Poropak Q
Chromosorb 103
Chromosorb 102
Tenax GC
Polyimide
Porapak Q
Thermal
Gradient
Dexil 300
Tenax GC
Dexil 300
Dexil 300
Tenax GC
Tenax GC
Dexil 300
Dexil 300
Tenax GC
Cylinder Pressure
in. Hg, Vacuum
Initial
28.6
28.8
28.5
28.6
28.6
28.6
28.8
28.7
28.7
Final
20.2
20.6
20.3
20.4
20.4
26.9
20.6
20.5
20.5
Temperature, °F
Initial
65
65
66
65
64
66
67
63
63
Final
67
67
68
68
67
67
68
65
65
Sampling
Time,
sec .
1091
1214
1151
1117
1143
639
1199
1256
1137
Sample
Volume,
SCF
0.119
0.116
0.116
0.116
0.116
0.0242
0.116
0.116
0.116
rv>
a
Collection tube partially plugged.
Sampling Conditions:
Nitrogen Flow = 50 cfh
Cylinder Volume = 0.421 cu.ft.
Barometric Pressure = 29.53 in. Hg first 4 runs
29-14 in. Hg last 6 runs
-------
were extremely complex. In most instances, a broad envelope
of unresolved peaks was obtained which was similar to those
experienced in the case of hydrocarbon fuels, excepting that
the present samples cover a much larger range of compound
types. GC/MS analysis was performed without the benefit of
samples for development of analytical conditions. A single
column for the adequate separation of these components,
which range in boiling points from -88°C to nearly 200°C,
might not have been available anyway.
The identification of all compounds present in the samples
was not accomplished. Major compounds present within various
areas of the chromatographic trace have been established,
however.
The total weight of each group of such compounds has been
estimated using peak areas. No specific correction has been
applied for the various compound types. Estimates, however,
are probably accurate to within the one significant figure
reported.
Groups of compounds and their identifying letters are:
A - Ethane, formaldehyde
B - Propane, methanol, carbonylsulfide
C - Butene, butane, sulfur dioxide, ethanol
D - Acetaldehyde
E - Furan, acrolein, propionaldehyde
F - Pentane, pentene, other C 's
G - Butyraldehyde
H - Hexane, hexene, Cg's, methacrolein
I - Methyl furan
J - Dimethylfuran, C~ hydrocarbons
23
-------
K - Benzene
L - Cg hydrocarbons
M - CQ hydrocarbons
N - Toluene
0 - Clf) hydrocarbons
P - Xylenes
Table 7 presents the milligrams of organics found in each
compound group.
-------
Table 7. ANALYSIS RESULTS - PLANT B COLLECTOR TUBES
Collector Pairs (Ambient
Temperature Collector/
Thermal Gradient Tube)
Chromosorb 102/
Dexil 300
Chromosorb 102 /
Tenax GC
Porapak Q/
Dexil 300
Porapak Q/
Tenax GC
Tenax GC/
Dexil 300
Tenax GC/
Tenax GC
Chromosorb 103/
Dexil 300
Chromosorb 103/
Tenax GC
Polyimide/
Dexil 300
Estimated Weight (mg) in Compound Groups-
A
0.06
0.007
0.05
0.20
.0.2
0.2
0.004
0.03
0.08
0.04
0.2
0.05
0.02
0.03
0.02
0.2
0.2
B
0.2
0.4
0.5
1.9
0.6
0.8
1.2
0.3
0.2
0.04
0.4
0.6
0.2
0.4
0.3
0.3
0.7
0.8
C
0.9
1.4
0.4
1.0
2.4
0.2
3.0
0.08
0.6
0.8
0.6
0.8
0.9
0.5
1.0
0.6
0.8
D
0.03
0.05
0.1
0.08
0.3
0.06
0.3
0.2
0.5
0.01
0.6
0.3
E
2.0
1.9
1.1
0.2
0.9
0.3
0.7
0.5
0.4
0.3
0.6
0.2
0.2
0.3
F
0.5
0.2
1.9
2.9
1.0
0.05
0.9
0.02
0.6
0.6
0.5
0.2
0.6
0.3
0.8
G
0.1
0.5
0.4
0.3
0.06
0.1
0.2
0.3
-
H
0.6
0.2
1.4
1.0
0.4
0.09
0.4
0.3
0.4
0.6
0.1
0.6
0.2
0.8
I
0.9
0.2
1.9
1.0
0.6
0.3
0.1
0.5
0.5
0.2
0.6
0.2
0.1
J
0.6
0.1
1.9
0.5
0.5
0.3
0.4
0.4
0.6
0.6
0.2
0.9
K
1.5
1.9
0.9
0.6
0.5
0.5
1.2
0.1
1.1
0.1
1.0
L _j
;
-
0.1
0.2
0.3
-
0.5
0.6
0.3
M
0.3
1.4
0.06
0.1
0.1
0.3
0.4
0.4
0.1
0.1
0.9
N
0.9
1.9
0.06
0.1
0.4
0.4
0.5
0.4
0.1
1.0
0
0.3
1.9
0.6
0.5
—
-
0.3
0.3
0.2
0.5
P
0.3
1.9
0.4
0.3
0.3
0.3
0.3
0.2
0.3
1.0
v_n
NOTE: Higher hydrocarbons in the C^. to C , range were detected above group P.
-Normalized for 0.116 SCF sample.
-------
SECTION VII
ANALYSIS OF DATA AND DISCUSSION
Since the thermal-gradient tube was designed to sample trace
organic material that was not absorbed by the ambient col-
lector tube, the total weight of organics in each collector
pair was examined.
It would be expected that the sum of the individual species
concentrations found in the paired tubes and that of the
total hydrocarbons would be equal for all combinations of
ambient temperature collector and thermal gradient tube.
Tables 8 and 9 present the summed data as pairs by individual
species and total hydrocarbons for Plants A and B, respec-
tively.
Examination of the data in Table 8 indicated that the total
hydrocarbon results from samples 6, 9, and 10 were not with-
in 2a of the mean total hydrocarbon value for all collector
pairs. After discarding these runs, the error for total
hydrocarbons in the remaining seven sampling runs was 2^%
at the 95% confidence limit.
A similar analysis of the data from Plant B indicated that
run 2 should be disqualified as an outlier. This pair of
collection tubes became plugged during sampling and sampling
was discontinued with only 21% of the desired sample volume.
For Plant B, the error at the 95% confidence limit for total
hydrocarbons collected was found to be 19$-
For organic emission compositions as complex as those charac-
teristic of the two sources sampled, the performance of the
dual adsorber system appears to be quite adequate.
26
-------
Table 8. STATISTICAL ANALYSIS OF TOTAL COLLECTION BY PAIRS - PLANT A
Collector Pairs
(Ambient Temperature Collector/
Thermal Gradient Tube)
1. Chromosorb 102/Dexil 300
2. Chromosorb 102/Tenax GC
3. Porapak Q/Dexil 300
4. Porapak Q/Tenax GC
5. Tenax GC/Dexil 300
6. Tenax GC/Tenax GC
7. Chromosorb 103/Tenax GC
8. Chromosorb 103/Tenax GC
9. Polyimide/Dexil 300
10. Polyimide/Dexil 300
Micrograms Collected
Ethane/
Ethylene
0.47
0.09
1.0
1.7
-
0.21
0.63
0.90
0.1
-
Propane/
Propylene
74
39.3
37.9
55
35.2
0.42
65
49.8
2.88
3.8
Acetal-
dehyde
2.0
1.5
2.9
1.2
2.01
-
2.3
1.8
0.4
0.4
Butane/
Butene
6.2
7.1
6.2
10.5
10.7
-
11.1
1.7
0.24
0.48
Acrylo-
nitrile
0.4
0.49
-
0.49
0.3
-
0.4
0.1
0.73
0.18
Methacrylo-
nitrile
0.01
0.6
1.0
0.4
0.4
-
0.78
0.15
0.2
0.7
Benzene
6.7
6.2
-
7.64
5.1
-
5.8
0.5
0.23
1.22
Total
Hydrocarbons
89.78
55.28
49.00
76.93
53.71
0.63
86.01
54.95
4.78
6.78
-------
Table 9. STATISTICAL ANALYSIS OF TOTAL COLLECTION BY PAIRS - PLANT B
Collector Pairs (Ambient
Temperature Collector/
Thermal Gradient Tube)
Chroraosorb 102/Duxil 300
Chromosorb 102/Tenax GC
Porapak Q/Dexll 300
Porapak Q/Tenax GC
Tenax GC/Dexil 300
Tenax GC/Tenax GC
Chroraosorb 103/Dcxll 300
Chromosorb 103/Tenax GC
Polylmide/DexlJ 300
A
0.067
0.25
0.2
0.204
0.12
0.24
0.07
0.05
0.4
Estimated Weight (mg) by Compound Groups
B
0.6
2.4
1.4
1.5
0.24
1.0
0.6
0.6
1.5
C
2.3
1.4
2.6
3.08
1.4
1.4
1.4
1.6
0.8
D
0.03
0.05
0.18
0.36
0.3
0.2
0.51
0.6
0.3
E
2.0
1.9
1.3
0.12
0.7
0.5
0.7
0.8
0.5
F
0.7
4.8
1.05
0.92
0.6
0.6
0.7
0.9
0.8
G
0.1
0.5
0.4
0.3
0.06
0.1
0.2
0.3
-
H
0.8
2.4
0.49
0.4
0.3
0.4
0.7
0.8
0.8
I
1.1
2.S)
0.6
0.3
0.1
0.5
0.7
0.8
0.1
J
0.7
2.4
0.5
0.3
0.4
0.4
0.6
0.6
1.1
K
1.5
1.9
0.9
0.6
0.5
0.5
1.3
1.2
1.0
L I
„
-
0.]
0.2
0.3
-
0.5
0.6
0.3
M
0.3
1.4
0.06
0.1
0.1
0.3
0.4
0.5
1.0
N
0.9
1.9
0.06
0.1
0.4
0.4
0.5
0.4
1.1
0
0,3
1.9
0.6
0.5
-
-
0.3
0.3
0.7
P
0.3
1.9
0.4
0.3
0.3
0.3
0.3
0.2
1.3
THC
n./o
28.00
10.84
9.28
5.82
6.84
9.48
10.25
11.70
t\J
CO
-------
The performance of the individual ambient temperature porous
polymer tubes varies according to the volatility and polar-
ity of the emitted species. This subject is addressed more
completely in Appendix D of this report. As is evident from
the data in Tables 3 and 7 the ambient collector tubes do not
exhibit a high efficiency in all cases. The failure of the
porous polymers to concentrate the hydrocarbons efficiently
is especially evident for the case of propane/propylene
analysis from Plant A (Table 3) and for the lower molecular
weight compound groups from Plant B (Table 7). In the later
case, for groups D through P the efficiencies of the ambient
collectors appear to be improved, with little organic emis-
sions breaking through to the thermal-gradient tube.
In both sources sampled non-oxygenated hydrocarbon emissions
predominated. Based on total hydrocarbons adsorbed by the
ambient temperature media, it is apparent that the experi-
mental polyimide performed very poorly. The performance of
the commercial porous polymers varied for the two plants.
For Plant A emissions, the first Tenax GC adsorption tube
(see Table 3) exhibited a higher total organics collection
followed by Porapak Q, Chromosorb 103 and Chromosorb 102.
In the case of Plant B emissions the decreasing order for
total organics collection was Porapak Q > Chromosorb 102 >
Chromosorb 103 > Tenax GC. The reversal of efficiency for
concentration of organics for Plants A and B by Tenax is
indicative of the variation in adsorption performance due
to the nature of the emissions composition.
29
-------
SECTION VIII
REFERENCES
1. Kaiser, R.E., Anal. Chem. 45, 965 (1973)
2. David, D.J. Gas Chromatographic Detectors, Wiley •
Interscience, New York, New York, 197^, pp. 67-68,
3. Ackman, R.G., J Gas Chromatog. 2, 173 (1964).
30
-------
APPENDICES
A. CHARACTERISTICS OP STATIONARY SOURCES EMITTING
ORGANIC SPECIES
B. ASSESSMENT OF PRESENT SAMPLING TECHNIQUES
C. USE OF POROUS POLYMER ADSORBENTS IN SAMPLING
D. CHARACTERISTICS OF POROUS POLYMER SORBENTS AND
POTENTIAL LIMITING PROPERTIES
E. REFERENCES CITED IN APPENDICES
31
-------
APPENDIX A
CHARACTERISTICS OF STATIONARY SOURCES
EMITTING ORGANIC SPECIES
The use of porous polymer packed adsorption tubes seems to be an
attractive approach to field sampling of organic emissions. How-
ever, the potential utility of these tubes depends on the ability
of the polymer materials to withstand the adverse conditions char-
acteristic of industrial sources emitting the organic materials.
Table 1 presents a matrix of industrial processes which could
serve as point sources of organic emissions. The emission char-
acteristics are presented in terms of composition, humidity, acid
content, temperature, pressure and flow rate. While this table
presents only a cursory view of the emission sources, it can serve
as a frame of reference to identify potential problems in the
application of porous polymer-packed sampling tubes. Sources
that exhibit reactive emissions (NOX, S02, acids, oxidizing atmos-
pheres), elevated temperatures, and high water loadings would
have to be approached with caution to assure that the final analyses
were indicative of the trace composition of the organic emissions.
A partial list of organic emissions which have been identified as
pollutants (Ref. 1 and 2) is presented in Table 2. Industrial
operations which have been identified as sources of organic con-
taminants (Ref. 3) are presented in Table 3. These latter two
tables are presented solely to point out the magnitude of the
overall problem and underline the need for a relatively simple
but accurate sampling and analysis technique for organic emissions.
The successful application of solid sorbents for sampling and
analysis of organic emissions depends upon a knowledgeable appli-
cation of selected sorbents to each specific source. To accomplish
this, detailed knowledge of the sorbent limitations must be com-
bined with accurate engineering knowledge of the source charac-
teristics .
32
-------
TABLE 1
CHARACTERISTICS OF POTENTIAL ORGANIC EMISSION SOURCES
oo
uo
Potential Organic
Emission Sources Part .
Storage Tanks
Unloading Facilities
Chemical Reactors
Non-Catalytic
Catalytic
Fluidized Bed
Fixed Bed
Moving Bed
Distillation Column
Flash Separator
Filters
Pressure Leaf
Filters
Rotary Vacuum
Filters
Nutsche Filters
Horizontal Plate
Filters
Tubular Filters
Bag Filters
Mixers
Grinders
Crushers
Scrubbers
Dryers
Counter-Current
Dryer
Rotary Drum
Dryer
Vacuum Rotary Dryer
Spray Dryers
Screeners
Vacuum Jets
X
X
X
X
x
X
x
X
X
X
X
X
X
X
X
Composition
NOy SO,, CO
X
X
X
X
X
X
XXX
XXX
XXX
XXX
XXX
X X
11C
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Temperature,
Humidity (% RH) Acid Content °F
0-20
0-20
0-20
0-20
0-20
0-20
0-98
0-98
0-98
0-98
0-98
0-98
0-98
0-98
0-20
0-20
0-20
80-95
0-9'j
0-95
0-95
0-95
0-20
•15-99
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-5t
-5H
-20
0
0
0
80
-48
70
70
70
70
70
70
32
32
32
60
100
100
100
100
32
270
- 300
- 200
- 1000
- 300
- 300
- 300
- 250
- 300
- 150
- 150
- 150
- 150
- 150
- 150
- 90
- 90
- 90
- 150
- 300
- 300
- 300
- 300
- 100
- 390
Pressure ,
psie
0-2
0-2
0-J'iOO
0-50
0-50
0-50
0-50
0-50
0-10
0-20
0-10
0-10
0-10
0-10
0-2
0-2
0-2
0-10
0-20
0-20
0-35
0-20
0-2
25-200
Flow Rate,
scfm
<100
<10r>
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10, onn
100-10,000
100-10,000
100-10,000
>10,000
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
>in,000
-------
TABLE 1 (Cont'd)
CHARACTERISTICS OF POTENTIAL ORGANIC EMISSION SOURCES
U)
-Cr
Potential Organic
Emibsion Sources
Waste Incinerators
Utility Boilers
Pneumatic Conveyors
Conveyor Belts
Extruders
Pellltlzers
Paint Spray Booths
Ovens
Blenders
Cyclones
Extraction Towers
Flares
Baggers
...oading; Facilities
Pooling 'Powers
Sett i ing Ponds
Evap< 'ators
Leaching Vat
Cookers
Refrigeration
Machines
Part.
X
X
X
X
X
X
X
X
X
X
X
X
Composition
NOX SOX CO HC Humidity (% RH)
X X V X
X X X X
X
X
X X X X
X
X
X X X X
X
X
X
X X X X
X
X
X
X
X
X
X X X X
10-95
10-95
10-30
0-20
0-20
0-20
0-20
0-50
0-20
0-20
0-90
10-95
0-20
0-20
40-95
10-95
0-95
0-95
0-95
0-10
Temperature,
Acid Content °F
X 500 -
500 -
X 10 -
32 -
100 -
100 -
60 -
500 -
32 -
70 -
X 70 -
1500 -
100 -
X -51 -
32 -
X 32 -
X 100 -
X 100 -
X 100 -
-50 -
1500
1500
90
90
350
200
100
1500
90
150
300
3000
200
300
100
8u
200
200
300
32
Pressure,
pale
0-5
0-5
0-20
0-2
0-2
0-2
0-5
0-2
0-2
0-20
0-50
0-2
0-2
0-2
0-2
0-2
0-50
0-2
0-2
50-300
Flow Rate,
scfm
>10,000
>10,000
>10,000
<100
<100
<100
>10,000
>10,000
100-10,000
10,000
100-10,000
>10,000
<100
<100
100-10,000
100-10,000
100-10,000
100-10,000
100-10,000
<100
-------
TABLE 2
ORGANIC SPECIES IDENTIFIED AS POLLUTANTS
A. OLEFINS
ethylene
propylene
1-butene
isobutene
1-pentene
2-methyl-1-butene
3-methyl-l-butene
1-hexene
2-ethyl-l-butene
2-methyl-l-pentene
2,3-dimethyl-l-butene
3,3-dimethyl-l-butene
1-heptene
2-methyl-1-hexene
1-octene
trans-2-butene
cis-2-butene
trans-2-pentene
cis-2-pentene
2-methyl-2-butene
trans-2-hexene
trans-3-hexene
trans-4-methyl-2-pentene
cis-4-methyl-2-pentene
2,3-dimethyl-2-butene
2-methyl-2-pentene
trans-2-heptene
trans-3-heptene
2-methyl-2-hexene
3-ethyl-2-pentene
2,3-dimethyl-2-pentene
trans-4-octene
2-methyl-2-heptene
pinene
2,3-dimethyl-2-hexene
cyclopentene
1-methylcyclopentene
cyclohexene
1-methyl cyclohexene
1,2-dimethyl cyclohexene
1,3-butadiene
2-methyl-l,3-butadiene
B. AROMATICS
benzene
toluene
p-Xylene
o-Xylene
m-Xylene
Ethyl benzene
1,2,4-trimethyIbenzene
1,2,3-trimethyIbenzene
1,3,5-trimethyIbenzene
isopropyIbenzene
1,3-methylethyIbenzene
t-butyIbenzene
1,2-diethyIbenzene
1,4-diethyIbenzene
1,3-diethyIbenzene
1,2,3,4-tetramethyIbenzene
1,2,3,4,5-pentamethylbenzene
styrene
cumene
methylstyrene
C. ALKANES
methane
ethane
propane
n-butane
isobutane
2,2-dimethylpropane
n-pentane
isopentane
n-hexane
2-methylpentane
3-methylpentane
2,2-dimethylpentane
2,3-dlmethylpentane
n-heptane
2,4-dimethylpentane
n-octane
3-methylheptane
isooctane
n-nonane
2,2,5-trimethylhexane
cyclopentane
methylcyclopentane
cyclohexane
35
-------
TABLE 2 (Cont'd.)
ORGANIC SPECIES IDENTIFIED AS POLLUTANTS
D. ALCOHOLS
raethanol
ethanol
D-butyl alcohol
isopropanol
n-butyl alcohol
isooctyl alcohols
octyl decenol
2-ethyloctanol
ALDEHYDES
acrolein
C8aldehydes
crotonaldehyde
formaldehyde
acetaldehyde
propionaldehyde
HALOGENATED COMPOUNDS
methyl chloride
methylene chloride
chloroform
carbon tetrachloride
allyl chloride
trichloropropane
epichlorohydrin
chlorobenzene
chloroethane
dichloroethane
trichloroethane
benzyl chloride
vinyl chloride
tetrachloroethylene
phosgene
ethylene bromide
methylbromine
chlorinated camphene
ESTERS AND ETHERS
acetone
ethyl acetate
methyl methacrylate
diethyl ether
methyl ethyl ketone
isopropyl acetate
ethyl acrylate
n-butyl acetate
diisopropyl ether
vinyl acetate
diethyl ketone
ethyl butyrate
H. ACIDS & ANHYDRIDES
acetic acid
phthalic anhydrides
male!c acid
benzoic acid
acrylic acid
fumaric acid
butyric acid
acetic anhydride
oleic acid
lactic acid
toluenesulfonic acid
NITROGEN COMPOUNDS
acrylonitrile
acetonitrile
aniline
nitrochlorobenzene
toluene diisocyanate
methylene dianiline
dinitrobenzene
trimethylamine
nitrobenzene
dimethylformamide
-------
TABLE 2 (Cont'd.)
ORGANIC SPECIES IDENTIFIED AS POLLUTANTS
J. MISCELLANEOUS
acetylene
propylene oxide
phenol
propylene glycol
nonylphenol
glycerol
hydroquinone
bisphenol A
naptha
hydrocarbons
37
-------
TABLE 3
ALPHABETICAL LISTING OF ORGANIC EMISSION SOURCES
Acetaldehyde - Hydration of Ethylene
Acetic Acid - from Acetaldefiyde
Acetic Acid - Carbonatlon of Methanol
Acetic Acid - Oxidation of Butane
Acetic Anhydride - from Acetic Acid
Acetone - from Cumene
Acetone - from Isopropanol
Acetone Cyanohydrln
Acetylene
Acrolein
Acrylic Acid - Propane Oxidation
Acrylonitrile
Acrylonitrile-Butadiene-Styrene Resins
Adiplc Acid
Adiponitrile
Alcohol Sulfates - Ammonium Salt
Alcohol Sulfates - Sodium Salt
Alcohol Sulfates - Triethanolamine Salt
Alkyd Resins
Allyl Chloride
Amino Resins
Aniline
Anthelmintics
Ascorbic Acid
Asphalt Paving - Hot Mix
Asphalt Roofing
Aspirin
Benzene - Coal Tar
Benzole Acid
Benzyl Chloride
Bis-Phenol-A
Bromomethane - Methyl Bromide
Butadiene
Butoxyethanol
n-Butyl Acetate
n-Butyl Acrylate
n-Butyl Alcohol
sec-Butyl Alcohol
t-Butyl Alcohol
Butyl Octyl Phthalate
Butylene Dimer
n-Butyraldehyde (oxo reaction)
Caprolactam - from Hydroxylamine
Carbon Black - furnace
Carbon Black - thermal
Carbon Disulfide
Carbon Tetrachloride - Chlorination of Carbon Bisulfide
Carbon Tetrachloride - Chlorination of Methane
Carbon Tetrachloride - Chlorination of Propane
Cellulose Acetate
Chlorinated Camphene
Chloroacetlc Acid
Chlorobenzene
2-Chloro-')-Ethylaniinoisopropylamlno Triazine
Chloroform
Chlorophenol
Chloroprene (from Butadlne)
Choline Chloride
Coffee Roasting
Cottonseed Oil Milling
Cresol - synthetic
Cresyldiphenyl Phosphate
Cresylic Acid
Crotonaldehyde
Cumene
Cumene Sulfonate - Hydrotrope
Cumene Sulfonic Acid
Cyclohexane
Cyclohexone
Cyclohexylamine
Cyclooctadiene
Decyl Alcohols
Deep Fryers
38
-------
TABLE 3 (Cont'd.)
ALPHABETICAL LISTING OF ORGANIC EMISSION SOURCES
Di Butyl Phthalate
o-Dichlorobenzene
p-Dichlorobenzene
Dichlorodifluoromethane
2,4-Dichlorophenoxyacetic Acid
2,'t-Dichlorophenoxyacetic Acid, Dimethylamine Salt
Di-2-Ethylhexyl Adipate
Di-(2-Ethylhexyl) Phthalate
Dlisodecyl Phthalate
Dllsooctal Phthalate
Dimethylhydrazlne - unsymmetrical
0,0-Dimethyl-o-p-Nitrophenyl-phosphorothioate
Dimethyl Phthalate
Dimethyl Terephthalate
Dinitrotoluene
Distilled Liquor
Dodecene
Dodecylbenzene - hard
Dodecylbenzene Sulfonic Acid
Eplchlorohydrin
Epoxy Resins
Ethanol
Ethanolamine
Ethoxyethanol
Ethoxylated Nonylphenol
Ethoxylated Octylphenol
Ethoxyethyl Acetate
Ethyl Acetate
Ethyl Acrylate- Carbonylation of
Acetylene
Ethyl Acrylate-Direct Esteriflcation
Ethyl Benzene
Ethyl Butyrate
Ethyl Chloride- Ifydrochlorination of
Ethylene
Ethyl Chloride- chlorination of Ethane
Ethyl Chloride- Hydrochlorination of
Ethanol
Ethyl Ether
Ethyl Hexanol
Ethylene
Ethylenediamine
Ethylene Dibromide
Ethylene Dichloride- Ethylene
Chlorination
Ethylene Dichloride- Oxychlorination
Ethylene Glycol
Ethylene Oxide
Ethylene - Fropylene Rubber
Ethylene Propylene Terpolymer Rubber
Fish and Sea Food Canning
Pood Preparation
Formaldehyde
Fruit and Vegetable Canning
Fruit and Vegetable Freezing
Fumaric Acid
Glycerin - .Acrolein
Glyerin - Allyl Ulcohol
Glycerin - Allyl Chloride
Glycerin - Epichlorohydrin
Glycerol, Tri - Polyoxypropylene Ether
Heptene
Hexachlorobenzene
Hexamethylenediamine - from Adiponitrile
Hexamethylenetetramine
Isocyanates
Isooctal Alcohols
Isophthalic Acid
Isoprene
Isopropanol - Direct Hydration
Isopropanol Acetate
Ketone Alcohol Oil
Leather
39
-------
TABLE 3 (Cont'd.)
ALPHABETICAL LISTING OP ORGANIC EMISSION SOURCES
Linear Alcohols- Zieglar Process
Linear Alkylbenzene
Malathion
Malelc Anhydride - from Benzene
Malt Beverage Production
Meat Smokehouse
Melaniine
Methanearsonic Acid - Calcium Acid Salt
Methanearsonic Acid - Dodecyl and Octyl
Ammonium Salts
Methanearsonic Acid - Disodium Salt
Methanearsonic Acid - Monosodium Salt
Methanol
Methoxyethanol
Methyl Acetate
Methyl Chloride
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Methyl Methacrylate - Cyanohydrin Proces"
Methylene Chloride - Chlorination of
Methane
Methylene dlphenyldiisocyanate
Mixed Linear Alcohols
Mixed Olefinite Product
Modacrylic Fibers
Monosodium Glutamate
Naphthalene - Coal Tar
Naphthonic Acid - Copper 6alt
1-Naphthyl-N-Methyl Carbonate
Nitroaniline
Nitrobenzene
Nitrocellulose
Nitrochlorobenzene
Nitroglycerine
Nitroparaffins
Nonene
Nonylphenol
Nylon 6
Nylon 66
n-Octyl-n-Decyl Phthalate
Octylphenol
Oleic Acid
italic Acid - Oxidation of Glucose
Oxo Mixed Linear Alcohols
Oxo Process
Paint Manufacturing *
n-Paraffin Chloride
Penicillin, G, Potassium
Penicillin, G, Procaine
Pentachlorophenol
Pentaerythritol
Pentaerythritol Tetranitrate
Perchloroethylene - Chlorination of Propane
Perchloro-ethylene - from Trlchloroethylene
Phenol-Cumene Process
Phenylmercuric Acetate
Phenylmercurlc Oleate
Phosgene
Phthalic Anhydride - from Naphthalene
Phthalic Anhydride - from 0-oxlene
Polyacrylonitrlle - Solution Polraerization
Polyamide Resins
Polybutadiene
Polycarbonate Resins
PC lychloroprene
Polyester Polyols
Polyester Resins
Polyethylene - High Density
Polyethylene - Low Density
Polyisobutylene - Isoprene - Butyl Elastomers
-------
TABLE 3 (Cont'd.)
ALPHABETICAL LISTING OF ORGANIC EMISSION SOURCES
Polylsoprene
Polyraethylene Polyphenyl Isocyanate
Polypropylene
Polyram
Polystyrene Resins
Polysulfide Rubber
Polyurethanes
Polyvlnyl Acetate
Polyvlnyl Alcohol - Hydrolysis
Polyvlnyl Chloride
Polyvinylvlnylidene Chloride
Printing Ink
Propionlc Acid
Propylene Glycol
Propylene Oxide - Chlorohydrin Process
Propylene Rimer + Tetramer
Rayon
Saccharin-o-toluenesulfonanites
Saccharin - from Phthalic Anhydride
Salicylates - excluding Aspirin
Salicylic Acid
Soap and Detergents
Solvent Evaporation - Degreasing
Solvent Evaporation - Dry Cleaning
Solvent Evaporation - Printing and Publishing
Solvent Evaporation - Rubber and Plastic Processing
Solvent Evaporation - Surface Coating Auto Painting
Solvent Evaporation - Surface Coating - Excluding Auto Painting
Sorbitol
Styrene
Styrene - Butadiene Copolymer Resins
Sugar Processing
Sulfated Ethoxylates
Sym-Trimethylene-Trinitramine
Terephthalic Acid
Tetracycline
Tetraethyl/Tetramethyl Lead
Tobacco
Toluenediaraine
Toluene Dlisocyanate
Toluene Sulfonate - Hydrotrope
Toluene Sulfonic Acid
1,1,1-Trichloroethane
1,1,2-Trichloroethane - from Ethylene Bichloride
Trichloroethylene - from Acetylene
Trichloroethylene - from Ethylene
Urea
Varnish Manufacturing
Vegetable Oil Milling
Vinyl Acetate - from Ethylene
Vinyl Acetate - from Acetylene
Vinyl Chloride - from Acetylene
Vinyl Chloride - from Ethylene Dichloride
Vinylidene Chloride - from Trichloroethane
Vitamin A
Vitamin B Complexes
Wet Corn Milling
Wood Processing - Kraft or Sulfate Process
Wood Processing - Neutral Sulfite Semi Chemical
Wood Processing - Sulfite Process
m-Xylene
o-Xylene
p-Xylene
Xylene Sulfonate-Ammonium Salt
Xylene Sulfonate Potassium Salt
Xylene Sulfonate - Sodium Salt
Xylene Sulfonic Acid
-------
APPENDIX B
ASSESSMENT OF PRESENT SAMPLING TECHNIQUES
The determination of a range of organic emissions from specific
sources is usually accomplished by sampling in the field and sub-
sequent analysis in the laboratory. Only in very special cases
is it feasible to monitor these emissions at the field site. One
case where this on-site monitoring was demonstrated was the use
of a chromatographic analyzer with flame photometric detector in
analysis of inorganic and organic sulfur species emitted from a
Kraft pulp mill (Ref. 4). However, in general, continuous or
intermittent monitoring of a range of organic species in the field
is not feasible due to the sophistication of laboratory instrumen-
tation required for analyses.
The detection and quantitative measurement of trace organic sub-
stances in gas phase mixtures, particularly ambient air and mobile
or stationary emission sources, generally requires a concentration
step to attain the required detection limit. The most frequently
employed concentration techniques are solvent scrubbing, con-
densation (cryogenic trapping), adsorption on activated carbon,
chromatographic adsorption, chromatographic equilibration, and
chemical reactions.
Solvent scrubbing for organics is achieved using an impinger train
containing a solvent system which will trap the desired emissions.
The train is often held at ice temperature to enhance collection
efficiency and minimize slippage of the desired components. De-
pending on the concentration of the emission, the flow rate and
the sampling time, the solvent must be reduced in volume to con-
centrate the pollutants before analysis. Evaporation of the
solvent runs the risk of significant losses in the more volatile
components of interest.
-------
Use of condensation techniques is the least desirable approach
since (a) collection efficiencies are poor and vary significantly
with physical and chemical properties of the substances being
collected, (b) condensation of water with attendent trap plugging
and hydrolysis of collected organics can occur, and (c) aerosols
(micro-fog) can form and not be trapped unless electrostatic pre-
cipitators are used. If significant amounts of moisture are
present, as is often realized in combustion, incineration or
absorber vent gases, the trap will contain a two-phase system which
will require special handling before analysis. Cryogenic trapping
at temperatures sufficient to condense oxygen or nitrogen requires
the use of special equipment to carry out analyses (Ref. 5).
Sample collecting and concentration techniques based on adsorption
on activated carbon have been used extensively. Activated charcoal
has been shown to quantitatively remove an extremely broad range
of organic contaminants from air. The National Institute of
Occupational Safety and Health (NIOSH) has promulgated a general
procedure for sampling and analysis of organics in work place
atmosphere (Ref. 6 and 7). This procedure is based on adsorption
of the organics on activated charcoal and desorption with carbon
disulfide followed by subsequent analysis by gas chromatograph.
While the adsorption process is quantitative, the recovery of the
collected components is usually incomplete and variable (Ref. 8).
The charcoal may also serve as a catalyst to promote alternation
of the sample (Ref. 9 and 10) and it is extremely subject to
adsorption of water vapor which limits the adsorption capacity
and can displace the desired organic components. Desorption by
heating requires high temperature (up to 400°C) and is accompanied
by chemical changes due to pyrolysis of the organic species and
thermally enhanced reactions between the components.
-------
Silica gel has been used for collecting three-carbon and higher
molecular weight hydrocarbons. The collection efficiency for
lower hydrocarbons, such as ethylene, from air has been demon-
strated to be poor even when trapping at dry ice acetone tem-
peratures (Ref. 11).
Short lengths of packed chromatographic columns commonly used for
the sepearation of hydrocarbons have been used to concentrate
aliphatic hydrocarbons at liquid-oxygen or liquid-nitrogen
temperatures (Ref. 12 - 16).
For specific applications, the chromatographie equilibration
technique (Ref. 17 - 19) can be employed. However, the major
limitation of this technique is the requirement that complete
equilibrium of adsorbate and gas-phase species be attained. With
the complex mixtures of source emissions, the potentially high
temperatures, and the problems of selective displacement of
volatile organics by less volatile species, the probability of
realistically attaining an adsorption equilibrium is questionable
in sampling source emissions.
GLC packings have been successfully employed for trapping and
concentrating aromatic hydrocarbons and organic oxygenenated
substances in ambient air on short sampling tubes (Ref. 17 -19).
This method of sampling avoids the use of cryogenic cooling and
special drying methods to remove atmospheric water. Cropper and
Kaminsky (Ref. 17) used a Celite 5^5 (30-60 mesh) support with
either Silicone Elastomer E301 or polyethylene glycol 400 as
stationary phases in short (1 inch) absorption tubes to concen-
trate a wide variety of organic substances at ambient temperature.
Retention volumes were determined for a range of organic vapors
to assess maximum permissable sampling times before break through
of the absorption tube occurred. Novak et al., (Ref. 18 and 19),
-------
used the identical GLC packings in 4.5 cm long tubes of 0.5 cm
diameter for sampling and subsequent GC analysis of nonpolar
(benzene, toluene and p-xylene) and polar(acetone, methanol and
toluene) mixtures in air. In this case the mean error was about
5% with concentrations from 1 to 25 ppm, and practical applica-
tions were demonstrated in the ppb range.
In certain applications, chemical reactions can be used to collect
and concentrate specific classes of chemicals and to desorb the
materials for analysis. Okita (Ref. 20) devised a field system
for sampling malodorous sulfur- and nitrogen-bearing organic gases
Mercuric salts were used to collect mercaptans and organic sul-
fides, while sulfuric acid was used as an impregnating agent to
glass fiber filters. By using the impregnated filters, sampling
flow rates of 1 to 14.5 1/min. with 97-100$ efficiencies of
collection and recovery can be used. In selected cases, sampling
rates as high as 100 1/min. can be used satisfactorily.
-------
APPENDIX C
USE OF POROUS POLYMER ADSORBENTS IN SAMPLING
Potentially, the most attractive method for collecting and concen-
trating organic substances from ambient air and mobile or station-
ary emission sources ^employs the adsorption and/or partitioning
properties of materials normally used in gas chromatographic
analysis to retain organic substances selectively while removing
the major diluent gases, such as air, nitrogen, and water vapor.
By proper selection of materials which retain little water,
separation of organic substances from water can be accomplished
even in samples taken in humid atmospheres. Various types of
chromatographic materials have been used, including carbon molecu-
lar sieves, liquid phases on solid supports, e.g., Dexil 300 GC
on Chromosorb AW HMDS and Silicone Oil DC 200 on Chromosorb, and
porous polymers such as Tenax GC and the Chromosorb and Porapak
series.
Williams and Umstead (Ref. 21) used porous polymer beads
(Porapak Q and S obtained from Waters Associates, Inc.) at room
temperature for concentrating organic vapors from air. The 80-
100 mesh Porapaks were contained in a 6-foot x 1/4-inch stainless
steel column which was later employed as the column in a chromato-
graph equipped with a Dohrmann microcoulometer detector. A wide
range of halogenated organic compounds were determined at air
concentrations as low as 10 ppb. The data showed that the col-
lection and analysis method was quantitative. Since the porous
polymer beads do not absorb moisture and readily pass the major
components of air and since they are amenable to on-column
injection to the detector, this method showed great promise for
analysis of organic air contaminants.
A number of workers have employed the porous polymer bead con-
centration approach in the last four years and have developed
-------
performance data for ambient air, blood, and urine analyses. Aue
and Teli (Ref. 22) prepared support-bonded chromatographic phases
such as (CiaH37Si03/2) on various types of Chromosorb to trap
organic vapors from the atmosphere. Using the silicone support-
bonded sorbents, gasoline, automobile exhaust, chlorinated hydro-
carbons, and contaminated air samples were sampled. In these
studies the trapped organics were extracted with pentane prior to
analysis. The method was found to be limited to higher molecular
weight species (>C6 organics), and some difficulties arose in the
occasional appearance of artifacts, possibly due to the incom-
plete removal of non-support-bonded silicone before sampling.
Dravnieks et al. , (Ref. 23) employed Chromosorb 102, a high sur-
face area styrene-divinyl copolymer porous polymer absorbent for
high speed (4l/min) collection of organic species from air. The
collection efficiencies of Chromosorb 102 for individual organic
species were compared to the respective partition coefficients.
In sampling from synthetic mixtures of nine components in air,
the reproducibility of the GC peak areas was within ±3%-
Zlatkis et al. , (Ref. 24) employed Tenax GC, a 2,6-diphenyl-p-
phenylene oxide porous polymer for sampling organic contaminants
in air, human breath, and urine. In these studies, the authors
compared the performance of Porapak P (a porous polymer of
styrene and divinyl benzene), Carbosieve (a carbon molecular
sieve), and Tenax GC in trapping organic contaminants. The
major drawback to the use of Porapak P is its temperature limit
of 230°C. This necessitates a maximum desorption temperatures
of 200°C at which temperature bleeding produced artifacts upon
analysis. Carbosieve, which is prepared by thermally cracking
polyvinylidene chloride, exhibited a high surface area (1000 m2/g)
and high temperature stability. Its major disadvantage is that
temperatures in excess of 400°C were needed to desorb organic
volatiles, and such conditions could cause pyrolysis of some
organics. In such cases, desorption by solvents may be required.
-------
Tenax GC appeares to fulfill both requirements, i.e., efficient
adsorptivity and desorptivity. It can withstand temperatures as
high as 375°C, permitting desorption at 300°C. The adsorption
tubes can be stored for long periods of time with excellent re-
producibility of data after subsequent desorption and chromato-
graphic analysis. In a later paper (Ref. 25) Zlatkis and coworkers
described use of the Tenax GC adsorption method in obtaining pro-
files of volatile metabolites of 150 urine samples from normal
subjects and 40 samples from individuals with diabetes. Char-
acteristic constituents in normal urines were 2-butanone, 2-
pentanone, 4-heptanone, dimethylsulfide, several alkyl furans,
pyrole, and carvone. For diabeties under insulin treatment, high
concentrations of pyrazines, cyclohexanone, lower aliphatic alcohols,
and octanols were found. These data point out the wide variety
of organic structures that are trapped by Tenax GC.
R. E. Kaiser (Ref. 26) conducted environmental analyses of organic
contaminants by using two different adsorption packings. Carbon
molecular sieve was employed to enrich ethylene or hydrocarbons
from methane to C^. Dexsil 300 GC (5% w/w on Chromosorb AW) was
used for enriching nonpolar and medium-polar impurities from C^ to
Ci5. Kaiser employed an adsorption tube with an imposed tem-
perature gradient (-20°C to -160°C for trapping; +250°C to +400°C
for elution) which led to a concentration focusing effect that
prevented chemical reaction of the enriched traces with one another.
This gradient enrichment approach also prevents micro-fog production,
which is a common source of error in cryogenic trapping systems.
Mieure and Dietrich (Ref. 27) employed a variety of porous polymer
adsorbents for determination of trace organics in air and water.
These investigators recommended Chromosorb 101 for sorption and
desorption of acidic and neutral components, Chromosorb 105 for
low boiling components and Tenax GC for basic, neutral and high
boiling species. As was the case with earlier workers, the ad-
sorption tube could be directly interfaced with a gas chromatograph
-------
either as an injection port Insert or as a connection directly
in the GC oven. Field sampling of ambient air at two liters/
minute flow rate over a 10-minute sampling interval was sufficient
to measure organic components at concentrations as low as 0.5
yg/m3 (1 ppb for a molecular weight of 100). Compound classes
determined in air in the vicinity of manufacturing sites included
phenols, alcohols, ketones, ethers, hydrocarbons, disulfides,
sulfur heterocyclics, aromatic amines, phthalate esters, and
chlorinated hydrocarbons. Corresponding classes determined in
wastewater included phenols, alcohols, nitro compounds, carboxylic
acids, aromatic amines, chlorinated hydrocarbons, esters, amides,
hydrocarbons, aliphatic amines, ethers, anilides, heterocycles,
aldehydes, ketones and sulfides.
Zlatkis and coworkers (Ref. 28 - 30) have published three recent
papers concerning use of Tenax GC for analysis of urinary meta-
bolites (Ref. 28), organic volatiles in air (Ref. 29), and trace
volatile metabolites in serum and plasma (Ref. 30).
It is evident from the above survey of recent publications that
the porous polymer bead adsorption sampling method shows great
promise for sampling of trace organic contaminants in ambient air
and is also attractive because the sampling tubes can be inter-
faced directly with laboratory analytical instrumentation such
as a gas chromatograph or a tandem-coupled gas chromatograph/mass
spectrometer system.
-------
APPENDIX D
CHARACTERISTICS OF POROUS POLYMER SORBENTS AND
POTENTIAL LIMITING PROPERTIES
As discussed in the previous section, various types of chromato-
graphic materials have been employed for sampling and subsequent
analysis of a range of organic pollutants. These include carbon
molecular sieves, liquid phases on solid supports, and porous
polymers.
The carbon molecular sieves (Carbosieves) can enrich ethylene or
hydrocarbons from methane to C4 from air, but suffer the same
desorption limitations as noted above for activated carbon. The
coated chromatographic packings lack retention capacity unless
cooled to subambient temperatures. With gradient cooling, however,
Dexsil 300 GC on Chromosorb AW HMDS provides sufficient retention
properties to enrich nonpolar and medium polar impurities in air
from Ci, up to C15 (Ref. 26).
The retentive characteristics, varied polarity, high-thermal
stability, and low affinity for water of porous polymers, suggest
that these materials might be the best media for efficiently
collecting and enriching organic substances in ambient air and/or
from mobile or stationary emission sources. However, the varied
nature of the emission sources requires an evaluation of the
limiting properties before specific applications can be defined.
The characteristics of typical porous polymers and their limiting
properties as sorbents are discussed in the following subsections.
The use of small tubes (4, 6 or 8 inches in length) packed with
porous polymer materials is an attractive approach to field
sampling. However, most sampling with these sorbents has been
done on ambient air, and their application to sampling stationary
source emissions has not been evaluated. MRC has used the porous
50
-------
polymer sampling techniques for collecting specimens and for
quantitative determinations of organic emission products from a
variety of major industrial paint and polymer-coating, drying or
processing, ovens (see Table 4). For applications to other
emission sources, which emit a more complex mixture or a more
reactive (temperature, oxidant, humidity, etc.) gas stream,
further evaluation is necessary.
The major problems related to the use of porous polymers as sor-
bents for collecting organic compounds from industrial emission
sources are:
(1) Displacement of more volatile species by less
volatile trace organics and/or by carbon-con-
taining gases (C02, hydrocarbons) which may be
the major components of the gas stream.
(2) Irreversible adsorption or poor desorption effi-
ciencies for certain specific compounds (e.g.,
amines, glycols, carboxylic acids, nitriles, high
molecular weight compounds).
(3) Chemical reaction of sorbates (e.g., oxidation,
hydrolysis, polymerization).
(4) Change in sorption properties of sorbent due to
interaction with reactive gases (e.g., NOX, SOX,
02, and inorganic acids, and depolymerization).
(5) Artifact species produced by action of reactive
gases and/or thermal effects.
(6) Retention capacity of the porous polymers.
(7) Thermal stability of sorbent.
(8) Sampling volume, flow rate, sampling time.
51
-------
TABLE
ORGANIC SUBSTANCES MEASURED BY MRC FROM PAINT
AND POLYMER CURING OVENS BY POROUS POLYMER
ADSORPTION AND SUBSEQUENT GC/MASS SPECTROMETRIC ANALYSIS
Methanol
Ethanol
Isopropanol
2-Ethoxyethanol
Isobutanol
n-Butanol
C5 Alcohols
n-Propanol
2-Methylbutanol
Ethyleneglycol monoethyl ether
2-(2-ethoxyethoxy) ethanol
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Methylethylketone
Dlethylether
Butylacetate
Sat. Hydrocarbons
2-Ethoxyethylacetate
Chloroform
Methylenechloride
Cyclohexane
DimethyIcyclohexane
Benzene
Toluene
Xylenes
Styrene
Methylstyrene
Dimethylstyrene
GS Alkylbenzenes
Cit Alkylbenzenes
Ci). Substituted Styrene
Trlchloroethane
Dlchloroethylene
Carbon Disulflde
Isopropylbenzene
Phenol
Benzaldehyde
1. PHYSICAL AND CHEMICAL CHARACTERISTICS OF POROUS
POLYMER SORBENTS
A variety of porous polymers have been developed for chromato-
graphlc purposes and have been used as collecting media for
organic substances. Although there are a number of variations,
the most used porous polymers are based on two or more monomer
systems, e.g., styrene or ethylvinylbenzene, divinylbenzene, and
a polar vinyl monomer. By varying the proportion of each monomer,
different polarity, thermal stability, surface area, pore size,
and retention characteristics can be obtained.
52
-------
Recently, Tenax GC, a new, more polar, and more thermally stable
porous polymer has become commercially available. This system is
based on 2,6-diphenyl-p-phenylene oxide. Other systems that have
been used in laboratory tests, but are not widely used or are not
commercially available, are polyimides, polyamides, polyacrylates,
and phosphonated or halogenated resins.
Four groups of porous polymers are potentially usable as sorbents
for collecting and concentrating organic compounds from stack
emissions. These are:
(1) Porapak series (Waters Assoc., Inc.)
(2) Chromosorb Century series (Johns-Manville Products
Corp. )
(3) XAD Resins (Rohm and Haas Co.)
(4) Tenax-GC (Enka, N.V., the Netherlands)
(5) Polyimides
Note: Some XAD resins are marketed by Johns-Manville
Products Corp. as the Chromosorb Century series;
e.g., Chromosorb 102 is XAD-2.
A limited amount of information is available which directly com-
pares the chromatographic properties of these materials. Re-
tention indices obtained under similar operating conditions are
reported for two groups, namely, the Porapak and the Chromosorb
Century series. Compilations of chromatographic retention data
(Ref. 31 - 33) for various chemical classes are reported and
compared for the most used resins in the Chromosorb and Porapak
series. The retention times (< 1 min to 260 min) of 90 organic
compounds (MW 32 to 162) including a variety of alcohols, ethers,
esters, dioxane, and dioxolanes are reported by Burger (Ref. 3D
for Porapak Q (2 ft x 3/16 in.) at l63°C.
53
-------
In general, the retention characteristics of the porous polymers
are influenced by both gas-solid and gas-liquid mechanisms. The
pore size distribution and micropore volume, the nature of the
polymer, and the surface activity all influence the adsorption,
diffusion, and partitioning processes. Although specific re-
tention indices are not available for all porous polymers, certain
physical property data and a relative ranking of polarity can de-
scribe the relative retention characteristics. These data are
shown in Tables 5, 6 and 7-
1.1 Chromatographic Characteristics of Porapak Resins
Porapak P
Least polar. Separates a wide variety of carbonyl com-
pounds, glycols, and alcohols.
Porapak P-S
Surface-silanized version of "P" which minimizes tailing.
Separates aldehydes and glycols.
Porapak Q
Most widely used. Particularly effective for hydro-
carbons, organic compounds in water, and oxides of
nitrogen.
Porapak Q-S
Surface-silanized version of "Q" which eliminates tailing.
Separates organic acids and other polar compounds with
minimum tailing.
Porapak R
Moderate polarity. Long retention and good resolution
observed for ethers. Separates esters, and H20 from
C12 and HC1.
-------
Ul
U1
TABLE 5
PROPERTIES OF PORAPAK SERIES POROUS POLYMERS
Porapak
Type
P
P-S*
Q
Q-S*
R
S
N
T
Surface Area
(mVg)
110
-
840
-
780
670
437
450
Ave . Pore Diam.
(A)
150
-
75
-
76
76
-
91
Temp. Limit
(°C)
250
250
250
250
250
250
190
190
Monomer
Composition
STY-DVB
•
EVB-DVB
-
Vinyl pyrollidone
Vinyl pyridine
Vinyl pyrollidone
Ethyleneglyco-
dimethylacrylate
*P-S and Q-S are silanized modification of P and Q, respectively
-------
TABLE 6
PROPERTIES OF CHROMOSORB CENTURY SERIES POROUS POLYMERS
Porous Polymer Surface Area Ave. Pore Diam. Temp. Limit
— i i , \ /Q\ / o n \
Monomer
Composition
•*• J t* *•* \ *'» ' t> / \ ** /
Chromosorb 101 30-40 3000-4000
Chromosorb 102 300-400 85
Chromosorb 103 15-25 3000-4000
Chromosorb 104 100-200 600-800
Chromosorb 105 600-700 400-600
Chromosorb 106
Chromosorb 107
Chromosorb 108
\ " f
275
(325)*
250
(300)*
275
(300)*
250
(275)*
250
(275)*
250
(275)*
250
(275)*
250
(275)*
STY-DVB
STY-DVB
Cross-linked
PS
ACN-DVB
Polyaromatic
Cross-linked
PS
Cross-linked
acrylic ester
Cross-linked
acrylic ester
STY-styrene; DVB-divinylbenzene; PS-polystyrene; ACN-acrylonitrile
*Maximum temperature for short duration
-------
TABLE 7
PROPERTIES OF XAD RESINS
ui
Porous Polymer
XAD-1
XAD-2
XAD-4
XAD-7
XAD-8
XAD-11
Surface Area
(mVg)
100
300
784
450
140
69
Ave . Pore Diam.
(A)
200
90
50
90
235
352
Temp. Limit
(°C)
200-250
200-250
200-250
200-250
200-250
200-250
Monomer
Composition
STY-DVB
STY-DVB
STY-DVB
Acrylic
Ester
Acrylic
Ester
Amide
-------
Porapak S
Separates normal and branched-chain alcohols.
Porapak N
Separates C02, NH3, and H20, and acetylene from other C2
hydrocarbons. High water retention.
Porapak T
Highest polarity and greatest water retention. Used for
determination of formaldehyde in aqueous solutions.
1.2 Chromatographic Properties of Chromosorb Resins
Chromosorb 101
Because of its surface nature Chromosorb 101 shows no interaction;
that is no tailing with oxygenated compounds, particularly hydro-
xyl compounds (alcohols, glycols, phenols) as well as carboxylic
acids. Chromosorb 101 is very effective in separating hydrocarbons,
alcohols, fatty acids, esters, aldehydes, ketones, ethers, and
glycols.
Chromosorb 102
Since Chromosorb 102 has a high surface area, it performs in a
manner similar to that of a conventionally packed column having a
high liquid phase loading. This characteristic causes retention
times on the column to be relatively high. Because of its high
surface area, Chromosorb 102 can be used to separate light and
permanent gases, as well as lower molecular weight compounds such
as acids, alcohols, glycols, ketones, esters, hydrocarbons, etc.
Chromosorb 103
Chromosorb 103 was developed specifically for amines and for basic
compounds. East, efficient separations are attained for amines,
amides, alcohols, aldehydes, hydrazines, and ketones. Chromosorb
103 will not handle acidic materials, glycols, or other compounds
58
-------
as acidic as glycols ; these are totally adsorbed. Methyl amine
is easily separated from light gases such as ammonia. There is
some tailing of water below 150°C.
Chromosorb
Chromosorb 104 is very efficient for gas analysis of various types
at subambient, ambient, and higher temperatures. It is also very
effective in separating isomeric xylenols, alcohols, ketones,
nitriles , aldehydes, and hydrocarbons. The important characteris-
tics of Chromosorb 104 are its effectiveness in separating sulfur-
containing compounds at low levels , aqueous ammonia and hydrogen
sulfide at low levels, isomeric xylenols, and gases of various
types. The retention times are longer on Chromosorb 104 than
other Chromosorb "Century Series" porous polymers. Chromosorb
104 has the highest polarity in the Chromosorb "Century Series"
porous polymers .
Chromosorb 105
The important characteristics of Chromosorb 105 are its effective-
ness in the separation of formaldehyde from water and methanol,
acetylene from lower hydrocarbons, and most other classes of
organic compounds of different polarity having a boiling point
up to 200°C. The polarity of Chromosorb 105 is lower than that
of Chromosorb 104.
Chromosorb 106
Chromosorb 106 retains benzene in relation to polar compounds
and separates C2 to C5 fatty acids from corresponding alcohols.
Chromosorb 107
Chromosorb 107 provides efficient separation of various classes
of compounds in general and formaldehyde in particular.
59
-------
Chromosorb 108
Chromosorb 108 is effective for separating gases and polar materials
such as water, alcohols, aldehydes, ketones, glycols, etc.
1.3 Chromatographic Properties of XAD Resins
Low molecular weight gases Ci-C2t are moderately retained at
ambient temperature on XAD resins. H2S is more strongly retained,
and sulfur dioxide, and vinyl chloride are strongly sorbed.
The more polar gases (H2S and S02) are more strongly sorbed on the
acrylate resins (XAD-7 and -8) and the phosphonated resin (XAD-1)
than on the STY-DVB resins. Ammonia also is retained longer on
the acrylates.
In a given XAD series, the retention times increase as the surface
area of the resins increase (Ref. 34). These findings are con-
trary to those of Johnson and Barrall for a series of Porapak
resins (Ref. 35). They found similar retention times for nonpolar
gases on four resins and concluded that the controlling factor
for separation is a function of the nature of the porous polymer,
rather than its micro-pore structure.
Increased temperature reduces the retention times and sharpens the
chromatographic peaks. For XAD-2 (2.5 ft x 1/4 in. with a flow
rate of 20 ml/min), typical retention times are 70 min at ambient,
19.0 min at 60°C, and 4.7 min at 100°C for vinyl chloride, and 40
min at ambient, 10.6 min at 60°C, and 2.70 min at 100°C for S02•
For Ci to C7 alcohols, an acrylic resin, XAD-7, has been used for
chromatographic separation. However, the alcohols are so strongly
retained that a high column temperature (programmed to 239°C) is
required for elution.
60
-------
1.4 Chromatographic Characteristics of Tenax GC
Tenax GC is a porous polymer that is based on 2,6-diphenyl-p-
phenylene oxide. It was developed originally for chromatography
of high boiling polar compounds such as alcohols, polyethylene
glycol compounds, diols, phenols, mono- and diamines, ethanol-
amine, amides, aldehydes, and ketones. It can also be used for
chromatography of lower boiling compounds such as methanol,
acetonitrile, methyl ethyl ketone, benzene, styrene, etc. The
resolution of these compounds is not as good for Tenax GC as for
Porapak Q. However, the thermal stability resulting in reduced
column bleed makes Tenax GC an excellent compromise for chroma-
tography samples containing organic compounds with a wide dis-
tribution of boiling points. In addition, Tenax GC is more stable
than most porous polymers due to its resistance to oxidation.
A recent paper by Butler and Burke (Ref. 36) discusses the rela-
tive sampling capacities for Tenax GC, Porapak, P, Q, R & T, and
Chromosorb 101 and 102. Their conclusion was that Porapaks Q
and R have the best overall sampling capacities and Tenax GC
should be used when higher boiling compounds are to be sampled
and analyzed. In addition, MRC's experience shows that the
greater thermal and oxidative stability of Tenax GC, compared
with the Porapaks Q and R, will result in lower levels of arti-
fact compounds being present in the analysis.
The surface area of Tenax GC is 19 mz/g and the temperature
limitation for its use is 375°C.
1.5 Chromatographic Characteristics of Polyimide Resins
An additional porous polymer system which is not presently
available commercially shows very high thermal stability (400°C)
and oxidative resistance. This system is based on polyimides
(Ref. 37). Two polymers of this type have been evaluated.
61
-------
Polysorbimide 1, formed from the reaction of pyromellitic
dianhydride and diaminodiphenyl ether, has a surface area of
67.5 m2/g and an average pore diameter of 2000 X. Polysorbimide 2,
formed from the dianhydride of benzophenone tetracarboxylic acid
and diaminodiphenyl ether, has a surface area of 41.8 m2/g and an
average pore diameter of 20,000 X. Both are macroporous sorbents
having large pore volumes. The high thermal stability extends
both the range of the compounds desorbed and the temperature of
desorption.
Some of their retention characteristics are:
(1) Saturated hydrocarbons, same as STY-DVB.
(2) Unsaturated compounds are more strongly retained.
(3) Retention of polar molecules depends on the dipole moment
and ability of compounds to form hydrogen bonds with the
sorbent surface.
(4) Specificity for molecular species, which is due to the
presence of imide and carbonyl functional groups on the
surface of the sorbents.
(5) Suitable for the separation of high boiling polar compounds
such as alcohols, esters, aromatic hydrocarbons, pyrrolidones,
aldehydes, and ketones (bp 200-300°C).
2. POTENTIAL LIMITING PROPERTIES OF POROUS POLYMERS AS SORBENTS
2.1 Displacement of Volatile Species
The displacement of volatile organic species by less volatile
organic substances is a major problem when using porous polymers.
High molecular weight compounds are more easily retained than low
molecular weight substances. Substances eluted before benzene
can be partially or completely lost. Bertsch, et al., (Ref. 29)
62
-------
have reported their inability to retain benzaldehyde, aceto-
phenone, and substances eluting before benzene on Tenax GC.
Data by Rabbani, et al., (Ref. 38) show that retention data of
different gases on porous polymers like porapak Q are influenced
by the nature of the carrier gas. Slight dependence of retention
data was observed when using gases (H2, Ar, N2) which are physi-
cally sorbed; however, when using carbon-containing carrier gases
(C02, C2H2, or C3H6), a substantial decrease in retention volumes
was observed for both hydrocarbons and nonhydrocarbon gases. At
52°C, the retention volume for C3H8 changed from 430 with N2 as
carrier to 305 with C02 and 260 with C2H2.
Such differences also depend on temperature since greater dif-
ferences are found at lower temperatures, e.g., 20°C, lesser
differences at higher temperatures, e.g., ?0°C, and much lesser
differences at 150°C. The effect is most critical at the lower
temperatures where the adsorption mechanism predominates, whereas
once the glass transition temperature for the polymer is reached
(^140°C), partitioning mechanism predominates. Based on these
data, when sampling C02 or hydrocarbon-rich emissions, some con-
sideration must be given to flushing effects when establishing
sampling times and rates.
2.2 irreversible Adsorption or Poor Desorption Efficiencies
Supina and Rose (Ref. 33) and Dave (Ref. 32) list retention data
for a wide variety of organic compounds. Information for the
Porapak (N, P, Q, R, S, T, QS) series and the Chromosorb Century
(101, 102, 103) series is provided. As derived from these in-
formation sources and general commercial literature, the most
pertinent data to use for porous polymers as adsorbents relate
to the chemical classes that cannot be desorbed from the resins.
Generally, the adsorption characteristics of most resins are
63
-------
adequate. However, some chemical classes are irreversibly ad-
sorbed or are desorbed slowly over a relatively long period.
The resins and associated chemical classes that will provide
potentially poor desorption efficiencies are as follows:
Glycols
Nitriles
Nitroparaffins
Amines and
diamines
Anilines
Carboxylic acids-
Complete adsorption on Chromosorb 103
Some tailing on Porapak Z, R, and S.
Severe tailing on Porapak QS
Severe tailing on Chromosorb 103
Severe tailing on Chromosorb 103
Severe tailing on Chromosorb 101 and 102
Porapak N, P, Q, R, S, T. Some tailing
on Porapak QS
Severe tailing on Porapak N, Q, S, T, QS
Some tailing on Porapak R
Complete adsorption on Chromosorb 103
Severe tailing on Porapak S. Some
tailing on Chromosorb 102 and Porapak Q
Some tailing on Porapak N. Branch-chain
broadening on Chromosorb 101, 102, 103
and Porapak T
A study by Hertl and Neumann (Ref. 39) established that extreme
tailing of amine peaks on Chromosorb 102 is due to unreacted
vinyl groups. A method was devised for removing these active
sites by adding HP to the double bond of the vinyl group. This
deactivation of Chromosorb 102 resulted in elimination or re-
duction of tailing for amine and pyridine peaks, but tailing of
acetic acid was increased by apparent interaction between the
carboxylic acid and surface fluoride groups.
Alcohols
-------
Peak broadening with branched hydrocarbons, alcohols, cycloalkanes,
sulfides, ketones, and fatty acids are reported for Porapak P and
PS, and Chromosorb 101 (Ref. 40).
Considerable irreversible adsorption difficulties can be encountered
when using some porous polymers; however, also significant is the
compatibility of the tubing and end plugs with the substance being
collected. For example, free carboxylic acids are strongly ad-
sorbed on metal column tubing, carbonaceous residues, as well as
glass wool used as column end-plugs. Silanized glass wool is
unsatisfactory; phosphoric acid appears to be the most effective
acid additive for treating glass wool. Glass column tubing does
not adsorb acids. Porapak Q, with added phosphoric acid to
suppress tailing, and Chromosorb 101 can be used to chromatograph
free acids (Ref. 4l).
2. 3 Chemical Reaction of Sorbates with Sorbents and
Production of Artifact Species
Porapak Q and Chromosorb 102 were found to react with N02 (Ref.
42) and oxygen (Ref. 43). The reaction with N02 yields NO, water,
and nitrated aromatic rings of the polymer plus the possible
presence of increased olefinic unsaturation and/or oxidation of
the polymer. Oxygen reacts with the resin above 100°C to
depolymerize part of it to produce carbonyl compounds.
In general, polystyrene-type materials suffer from oxidation and
thermal fragmentation at temperatures above 250°C.
2.4 Change in Sorption Properties of Porous Polymers
The reactions discussed above in 2.3 undoubtedly influence the
sorption properties of porous polymers. The displacement phe-
nomena indicated above in 2.1 also point out potential problems
-------
related to physical adsorption changes at collection temperatures
below l40°C, where the physical adsorption mechanism for compound
retention predominates with the STY or EVB-DVB systems.
Also, problems may be experienced when using porous polymers
under high-humidity, high-temperature conditions. Although Dave
(Ref. 32) reports that Chromosorb 101, 102, and 103, and Porapaks
N, P, Q, QS, R, S, and T are hydrophobic, and Bertsch (Ref. 29)
suggests that Tenax GC has little affinity for water. Certain
precautions must be considered in actual use. Steam displacement
of organic substances may occur, and some changes in the surface
adsorption sites (particularly with the more polar resins) may
result. Even with the more hydrophobic resins, e.g., Porapak Q
(EVB-DVB), some water is actually adsorbed. Porapak Q retains
up to 3.4 yg H20/g of polymer at 110°C (Ref. 44).
At present, it is generally assumed in a qualitative sense that
the interaction mechanism for adsorbates on porous polymers is
a combination of both adsorption and partitioning, especially at
higher temperatures. Below the glass transition temperature
(Tp.), absorption of organic vapors by porous polymers occurs
o
through very complex processes. Amorphous polymers would be
expected to absorb organic vapors to a much greater extent if
they were in a rubbery state as opposed to a glass. Data suggest
that surface adsorption should predominate for organic molecules
at temperatures below l40°C.
2.5 Retention Capacity of Porous Polymers
Pore size determinations for Porapak P and Q indicate that a large
proportion of very small pores exist in these resins, particularly
Porapak Q. As a result, a large portion of the "N2" surface area
reported by the manufacturers may not be available to the more
bulky organic molecules. Chromosorb 101 has relatively large
pores compared to the Porapak P and Q.
66
-------
Estimates of "available" surface area to organic molecules were
made by Gearhart and Burke (Ref. 45) for Chromosorb 102, Porapak
P, and Porapak Q. The basis for their estimates was the measure-
ment of free energy changes for molecular probe-adsorbent in-
teractions. By relating these measurements for benzene, cyclo-
hexane, cyclohexene, hexane, hexene, methylene chloride, and
chloroform, estimates of "available" surface area were computed.
Chromosorb 101 was used as a norm for comparison since it probably
has the greatest proportion of available surface area. The
apparent surface areas for Chromosorb 102, Porapak P, and Porapak
Q are 95, 37, and 133 m2/g, respectively. These estimates re-
present 33.7%, 27.1$, and 20.2% of the manufacturer's reported
surface areas.
2.6 Thermal Stability of Sorbent
Thermal stability of the porous polymer sorbent is critical
principally from the standpoint of the optimum temperature for
desorption. If relatively high molecular weight materials (e.g.,
MW 140) are to be measured, desorption temperatures as high as
290-300°C may be required. Obviously, lower molecular weight
materials will be desorbed at lower temperatures. The choice
of sorbent for a particular sorbate will depend in large part
on the temperature needed for desorption.
2. 7 Sampling Volume, Flow Rate, and Sampling Time
The sampling volume and sampling times will depend largely on
the concentration of species, the retention characteristics of
the sorbent, the gas stream temperature, and the composition of
the gas stream with reference to potential displacement mechanisms
The choice of sampling flow rate will depend on the retention
characteristics and volatility of the species being collected.
67
-------
Flow rates of 20-30 ml/min are preferred, but 50 to 200 ml/min
can be used as a compromise between time requirement and sample
loss. The volatile compounds, e.g., benzene, C9 and lower ali-
phatic or olefinic hydrocarbons, are only partially adsorbed at
high flow rates (200-1000 ml/min).
68
-------
APPENDIX E
REFERENCES CITED IN APPENDICES
1. Anon., "Hydrocarbon Pollutant Systems Study - Volume I -
Stationary Sources, Effects and Control," MSA Research
Corporation APTD 1499, 20 October 1972.
2. Ittel, S. D., D. B. Dahm and A. D. Snyder, "Behavior, Fate
and Effects of Atmospheric Pollutants - A Literature Survey,"
MRC-DA-287 (1968).
3. Anon., "Prioritization of Sources of Air Pollution," Monsanto
Research Corporation, EPA Contract 68-02-1320, 31 July 1976.
4. Stevens, R. K. and O'Keefe, A. E., Anal. Chem. 42_, 143A (1970).
5. Rasmussen, R. A., Am. Lab., December 1972, Page 55-
6. National Institute of Safety and Health, P & CM #127-
7. Mueller, F. X. and Miller, J. A., Amer. Lab., Pg. 49, May 1974
8. Jennings. W. G. and Nursten, H. E. , Anal. Chem. 39., 521 (1967)
9. Altshuller, A. P., Advan. Chromatogr. 5., 229 (1968).
10. Adams, D. F. , Koppe, R. K. and Jungrath, D. M., Tappi 43,
602 (I960).
11. Altshuller, A. P., Bellar, T. A. and Clemens, C. A., Am. Ind.
Hyg. Assoc. J 23., 164 (1962).
12. Eggertsen, F. T. and Nelsen, F. M., Anal. Chem. 30, 1040
(1958).
13. Farrington, P. S., Pecock, R. L., Meeker, R. L., and Olsen,
T. J., Anal. Chem. 31, 1512, (1959).
14. Neligan, R. E. , Arch Environ. Health 5., 58l (1962).
15. Bellar, T. A., Brown, M. F. and Sigsbey, J. E. Jr., Anal.
Chem. 3£, 1924 (1965).
16. Feldstein, M. and Balestrieni, S., Air Pollution Control
Assoc. 15, 177 (1965).
69
-------
17. Cropper, F. R. and Kaminsky, S. Anal. Chem. 35., 735 (1963).
18. Novak, J., Vasak, V. and Janak, J. Anal. Chem. 37., 661
(1965).
19. Gellucova-Ruzickova, J., Novak, J. and Janak, J., J. Chromatogr
64_, 15 (1972).
20. Okita, T. , Atmospheric Environ. 4_, 93-102 (1970).
21. Williams. F. E. and Umstead, M. E. Anal. Chem. 40, 2252
(1968).
22. Aue, W. A. and Tell, P. M., J. Chromatogr. 62, 15 (1971).
23. Dravnieks, A., Krotoszynski, B. K. Whitfield, J., O'Donnell,
A. and Burgwald, T. , Env. Sci. Tech. 5., 1220 (1971).
24. Zlatkis, A., Lichtenstein, H. A. and Tishbee, A., Chromato-
graphia 6_, 67 (1973).
25. Zlatkis, A., Bertsch, W., Lichtenstein, H. A., Tishbee, A.,
Shunbo, F., Liebich, H. M., Coscia, A. M. and Fleischer, H.,
Anal. Chem. 45., 765 (1973).
26. Kaiser, R. E., Anal. Chem. 4_5, 965 (1973).
27. Mieure, J. P. and Dietrich, M. W. , J. Chromatogr. Sci. 1.1,
559 (1973).
28. Zlatkis, A. , Lichtenstein, H. A., Tishbee, A., Shunbo, F.
and Liebich, H. M., J. Chromatogr. Sci. ri, 299 (1973)-
29. Bertsch, W., Chang. R. C. and Zlatkis, A., J. Chromatogr.
Sci. 12, 175 (1974).
30. Zlatkis, A., Bertsch, W. , Bakus, D. A. and Liebich, H. M.,
J. Chromatogr. 9_i, 399 (1974).
31. Burger, J. D., J. Gas Chromatogr. 6_, 177 (1968).
32. Dave, S. B. , J. Chromatogr. Sci. 7_, 389 (1969).
33. Supina, W. R. and Rose, L. P., J. Chromatogr. Sci. 7., 192
(1969).
34. Fritz, J. S. and Chang, R. C. , Anal. Chem. 46., 938-940 (1974).
35. Johnson, J. F. , Barrall, E. M. , J. Chromatogr. 3_i> 547 (1967).
70
-------
36. Butler, L. D. , and Burke, M. F., J. Chrom. Sci 14
117-122 (1976). —'
37. Sakodynsky, I. I., Kllnskaya, N. S., and Pahlna, L. I.
Anal. Chem. J»5_, 1369-1374 (1973).
38. Rabbanl, G.S.M., Rusek, M., and Janak, J., J. Gas Chroma-
togr. 6_, 399 (1968).
39- Hertl, W., and Neumann, M. G., J. Chromatogr. 60, 319
(1971). —
40. Ackman, R. G., J. Chromatogr. Sci. 10, 506-508 (1972).
41. Ottensteln, D. M., and Bartley, D. A., J. Chromatogr.
Sci. £, 673-681 (1971).
42. Trowell, J. M. , J. Chromatogr. Sci. 9_, 253 (1971).
43- Neumann, M. G., and Morales, S., J. Chromatogr. 74,
332 (1972). —
44. Gough, T. A., and Sampson, C. P., J. Chromatogr. 68,
31-45 (1973). —
45. Gearhart, H. L., and Burke, M. F., J. Chromatogr. Sci.
11, 411 (1973).
71
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-201
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Utility of Solid Sorbents for Sampling Organic
Emissions from Stationary Sources
5. REPORT DATE
July 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Arthur D. Snyder, F. Neil Hodgson,
M.A. Kemmer, andJ.R. McKendree
8. PERFORMING ORGANIZATION REPORT NO.
MRCDA # 567
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
P.O. Box 8 (Station B)
Dayton, OH 45407
1O. PROGRAM ELEMENT NO.
1AB013; ROAP 21ACX-094
1. CONTRACT/GRANT NO.
68-02-1411, Task 10
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final: 5/75-5/76
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES EpA project officer for this report is L.D. Johnson, Mail Drop
62, Ext 2557.
16. ABSTRACT
The report gives results of a study to assess the utility of porous polymer
adsorbents as a means of sampling and concentrating trace organic emissions from
stationary sources. Emissions from two industrial field sites were sampled, using
small porous polymer sampling tubes backed up by a cryogenic thermal-gradient
sampling system to assess the efficiencies of adsorption of the trace organic species.
In addition to experimental results, conclusions, and recommendations, a detailed
statement of the problem of sampling trace organics in industrial emissions is pre-
sented in the Appendices. This later discussion includes: the characteristics of
stationary sources emitting organic species; an assessment of present sampling
techniques for organic matter; a review of the use of porous polymer adsorbents in
sampling; and the characteristics of porous polymer sorbents and their potential
limiting properties.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air Pollution
Sampling
Organic Compounds
Sorbents
Polymers
Adsorption
Cryogenics
Air Pollution Control
Stationary Sources
Organic Emissions
Solid Sorbents
Porous Polymers
13B
14B
07C
11G
07D
20M
8. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
77
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
------- |