United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600/2-80-017
March 1980
Research and Development
Collection and
Analysis of
Purgeable Organics
Emitted from
Wastewater
Treatment Plants
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are: . . '" ..': ::' '. ::.: ::::':::::;::: :. ,::;::::::::':,:"::,:::',:::,;:::':":::
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4, Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental 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.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-80-017
March 1980
COLLECTION AND ANALYSIS OF PURGEABLE ORGANICS
EMITTED FROM WASTEWATER TREATMENT PLANTS
by
Edo D. Pellizzari and Linda Little
Research Triangle Institute
Research Triangle Park,' North Carolina 27709
Contract No. 68-03-2681
Project Officer
Hovjard 0. Wall and Dolloff F. Bishop
Wastewater .Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for use.
ii
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution of the health
and welfare of the American people. Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solu-
tion and it involves defining the problem, measuring its impact, and search-
ing for solutions. The Municipal Environmental Research Laboratory develops
new and improved.technology and systems for the prevention, treatment, and
management of wastewater and solid and hazardous waste pollutant discharges
from municipal and community sources, for the preservation and treatment of
public drinking water supplies, and to minimize the adverse economic, social,
health, and aesthetic effects of pollution. This publication is one of the
products of that research; a most vital communications link between the
researcher and the user community.
.The study describes the development of an analytical method for the
analysis of purgeable toxic organics which are air'stripped from wastewater
during treatment in wastewater treatment plants. The method is one of the
tools needed fco assess the fate and removability of priority organics enter-
ing wastewater treatment plants.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
iii
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ABSTRACT
An analytical method was developed for the analysis of volatile priority
pollutants in airstreams passing through wastewaters using a Tenax GC cart-
ridge in combination with gas chromatography/mass spectrometry/computer. A
sampling system was designed and field tested for sampling airstreams pas-
sing through grit chambers and activated sludge systems. Recovery of the
volatile priority pollutants was accomplished by thermal desorption, purging
with helium into a liquid^nitrogen^cooled nickel capillary trap, and intro-
ducing the vapors onto a gas qhromatographic column where they were separa-
ted from each other. Characterization and quantification of the priority
pollutants was accomplished by mass spectrometry using mass fragmentography.
The areas of investigation included: (a) the performance of a Tenax GC
sampling cartridge for the priority pollutants occurring in the airstreams
passing through wastewaters; (b) the design, fabrication and evaluation of a
field sampler; (c) recovery studies of priority pollutants from distilled
water, raw wastewater and activated sludge using laboratory-Simulated condi-
tions; (d) a methods-of-^addition study for priority pollutants in raw waste-
water and activated sludge; (e) the delineation of the GG/MS/COMP operating
parameters for priority pollutants collected on Tenax GC cartridges; (f) the
application of the developed methods to the analysis of priority pollutants
occurring in airstreams passing through raw wastewater and activated sludge,
and (g) evaluation of the accuracy and precision of the collection methods
for "purgeable" priority pollutants in airstreams from raw wastewater and
activated sludge basins.
This report was submitted,in fulfillment of Contract No. 68-03-2681 by
Research Triangle Institute under the sponsorship of the U. S. Environmental
Protection Agency.
iv
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CONTENTS
Foreword „ ill
Abstract iv
Figures vi
Tables x
Acknowledgements xii
1. Introduction 1
2. Conclusions 10
3. Recommendations. . 12
4. Program Objectives ...» 13
5. Evaluation of Tenax GC Sampling Cartridges for Use With
Priority Pollutants ...... 14
6. Recovery of "Purgeable" Priority Pollutants from Aqueous
Media 29
7. Design and Fabrication of Sampling System for Priority
Pollutants Emitted from Municipal Treatment Facili-r
ties. 53
8. Instrumental (GC/MS/COMP) Methods of Analysis. ...... 62
9. Application of Developed Methods to the Collection and
Analysis of "Purgeable" Priority Pollutants Emitted
From Municipal Treatment Facilities 71
10. Accuracy and Precision of "Purgeable" Priority Pollu-
tant Collection and Storage ..... 85
References 103
Appendices
A. Volatile Qrganics in. Air Stream from Grit Chamber 105
B. Volatile Organics in Air Stream from Aeration Pond . . . .142
C. Volatile Organics in Vent from Pure Oxygen (Closed
Chamber) System . .167
D. Analysis of Priority Pollutants in Airstreams from
Wastewater and Activated Sludge 171
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FIGURES
Number Pag£
1 Mason Farm Wastewater Treatment Plant 5
2 Flow diagram of Northside Sewage Treatment Plant, Durham, NC . 6
3 Water pollution control facilities, City of Danville, VA . . . 8
4 Thermal desorption inlet-manifold 17
5 Cryo-heater module for inlet-manifold 18
6 Permeation system for generating air/vapor mixtures 20
7 Sampler cartridge transport tube1 (Nutech Corp., Durham, NC). . 23
8 Vessel configuration employed in air-stripping experiments . . 30
9 Linear regressions (benzene, toluene, chlorobenzene, bromoform
ethylbenzene) for methods-of-addition study on raw waste-
water from Durham, NC Northside Treatment Plant 37
10 Linear regressions (trichloroethylene, 1,2-dichloropropane,
carbon tetrachloride, 1,2-trans-dichloroethylene) for
methods-of-addition study on raw wastewater from Durham,
NC Northside Treatment plant 38
11 Linear regressions (chloroform, bromodichloromethane, 1,1,2-
trichloroethylene, 1,2-dichloroethane, dichloromethane)
for methods-of-addition study on raw wastewater from
Durham, NC Northside Treatment plant 39
12 Linear regressions (acrylonitrile, 1,1-dichloroethane, 1,3-
dichlorobenzene, tetrachloroethylene) for methods-of-
addition study on raw wastewater from Durham, NC North-
side Treatment plant. . 40
13 Linear regressions (acrylonitrile, 1,3-dichlorobenzene, ethyl-
benzene) for methods-of-addition study on activated
sludge from Durham, NC Northside Treatment plant 42
14 Linear regressions (dichloromethane, bromodichloromethane,
bromoform) for methods-of-addition study on activated
sludge from Durham, NC Northside Treatment plant 43
15 Linear regressions (1,1,2-trichloroethylene, carbon tetra-
chloride, 1,2-dichloroethane, chloroform, 1,2-trans-
dichloroethylene) for addition study on activated
sludge from Durham, NC Northside Treatment plant 44
16 Linear regressions (benzene, 1,1-dichloroethane, toluene,
chlorobenzene 1,2-dichlorobenzene) for methods-of-
addition study on activated sludge from Durham, NC
Northside Treatment plant 45
17 Linear regressions (trichloroethylene, tetrachloroethylene,
1,2-dichloropropane, 1,1,1-trichloroethane) for methods-
of-addition study on activated sludge from Northside
Treatment plant 46
Vi
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FIGURES (cont'd.)
Number
18
19
20
21
22
23
24
25
Al
A2
A3
A4
A5
A6
A7
A8
A9
A10
All
A12
A13
A14
A15
A16
A17
A18
A19
A20
A21
A22
A23
A24
A25
A26
A27
A28
A29
A30
A31
Schematic of sampler system for grit chambers and aeration
tanks : . . 54
Schematic of sampling shroud 55
Diagram of pneumatics in sampler system 58
Schematic of electronics in sampler system. . . 59
GC/MS/COMP chromatographic profile of volatile organics iden-
tified in air stream from aeration pond at Durham, NC
Treatment plant , . 75
Vessel employed in radiolabeled priority pollutant studies. . . 87
Desorption apparatus for radioisotopically labelled com-
pounds on Tenax GC . 88
Diagram of pneumatics in sampler system 91
Reconstructed GC/MS chromatogram of volatile organics in air
stream from grit chamber at S. Burlington, NC Treatment
plant (Sample 1, 1.0 S-) .105
Reconstructed GC/MS chromatogram of volatile organics in air
stream from grit chamber at S. Burlington, NC Treatment
plant (Sample 2, 1.0 £) 106
Mass spectrum of peak at 2.0 min. . . 107
Mass spectrum of peak at 6.06 min . . . . . 108
spectrum of peak at 6.26 min 109
spectra, of peaks at 8.49 and 9.29 mins .110
spectra of peaks at 10.33 and 10.86 min. . . . Ill
10.33 min. . '. 112
12.46 and 13.19 min. 113
53 and 13.93 min . .114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
m/z 134, 186 134
m/z 91, 106. . . . . . . 135
Mass
Mass
Mass
Mass spectrum of peak at
Mass spectra of peaks at
Mass spectra of peaks at 13
spectra of peaks at
spectra of peaks
chromatograms
Mass chromatograms
Mass chromatograms
chromatograms
chromatograms
chromatograms
chromatograms
chromatograms
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
•Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
:s at 15.09 and
:s at 16.19 and
m/z 53, 84 . .
m/z 86, 96 . .
m/z 61, 83 . .
m/z 85, 96 . .
m/z 98, 100. .
m/z 97, 99 ..
m/z 117, 121 .
m/z 127, 172 .
m/z 79, 99 . .
m/z 112, 114 .
m/z 130, 132 .
m/z '134, 83. .
m/z 93, 164. .
m/z 166, 170 .
m/z 171, 91. .
m/z 106, 112 .
m/z 114, 120 .
15.26 min
18.03 min
vii
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FIGURES (cont'd.)
Number
A32
A33
A34
A35
A36
A37
Bl
B2
B3
B4
B5
B6
B7
B8
B9
BIO
Bll
B12
B13
B14
B15
B16
B17
B18
B19
B20
B21
B22
B23
B24
B25
01
C2
C3
C4
Dl
D2
D3
D4
D5
D6
D7
Mass chroma to grams - m/z 120, 134 .136
Mass chromatograms - m/z 126, 91 .137
Mass chromatograms - m/z 126, 128 138
Mass chromatograms - m/z 134, 91 139
Mass chromatograms - m/z 119, 120 140
Mass chromatograms - m/z 105, 120 141
Reconstructed GC/MS chromatogram of volatile organics in air
stream from aeration pond at S. Burlington, NC Treatment
Plant (Sample 1( 1.0 A) ' • 142
Mass chromatograms - m/z 53, 84 « 143
- m/z 86, 96 144
- m/z 83, 85 145
- m/z 96, 97. . 146
98 147
117 148
112 149
150
, 151
m/z 97,
m/z 100,
m/z 97,.
m/z 121
m/z 127,
78
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatogram
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms - m/z
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatograms
Mass chromatogram - m/z 120
Mass chromatograms - m/z 91, 126
m/z 79, 97 152
m/z 130, 132 153
171, 83 154
m/z 83, 164 155
m/z 166, 170 156
m/z 171, 186 .157
m/z 91, 106 158
m/z 105, 120. 159
m/z 112, 114 160
m/z 236, 91 . . . 161
m/z 105, 106 162
163
164
Mass chromatograms - m/z 128, 105 165
Reconstructed GC/MS chromatogram of volatile organics in air
stream from aeration basin at Durham, NC Treatment plant. .166
Reconstructed GC/MS chromatograms for volatile organics in
vent of closed chamber at Danville, VA Treatment plant.
Mass spectrum of peak at 41.03 min . .
Mass chromatogram - m/z 120, 105 • •
Mass chromatograms - m/z 120, 119
.167
.168
.169
.170
Schematic of sampler system for grit chambers and aeration tanks!77
Schematic of sampling shroud 178
Diagram of pneumatics in sampler system .179
Schematic of electronics in sampler system -180
Permeation system for generating air/vapor mixtures. ..... .182
Sampler cartridge transport tube (Nutech Corp., Durham, NC). . ,184
Sampler schematic for closed chamber systems 187
Viii
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FIGURES (cont'd.)
Number
D8
D9
D10
Dll
Total ion current profile for volatile priority pollutants
collected from air stream through raw wastewater at
South Burlington, NC waste treatment plant 194
Ion chromatograms for 1,2-dichlorobenzene in sample taken from
air stream through raw wastewater at South Burlington,
NC waste treatment plant 195
Total ion current profile of Tenax cartridge blank 196
Field sampling protocol sheet - A 197
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TABLES
Number
1
2
3
4
5
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Parameters for Inlet-Manifold and Gas-Liquid Chromatography.
Permeation Tubes for Several Volatile Priority Pollutants. .
Breakthrough Volumes for Several Priority Pollutants ....
Recovery of Priority Pollutants from Stored Tenax Cartridges
Relative Recoveries for Wet Vs Dried Samples Using CaSO, for
2 Hr . . . .
Relative Recoveries of Wet Vs Dried Samples as a Function
of Storage Time .
19
21
24
26
27
28
Operating Parameters for GC-MS-COMP System 33
Percent Recovery of Priority Pollutants from Deionized/Dis-
tilled Water for Three Vessel Configurations. ....... 34
Methods-of-Addition Study for Priority Pollutants from Raw
Wastewater 36
Methods-of-Addition Study for Priority Pollutants from
Activated Sludge 41
Percent Recovery of Priority Pollutants from Raw Wastewater
from Grit Chamber at Durham Waste Treatment Plant .... 47
Percent Recovery of Priority Pollutants from Activated Sludge
at Durham Waste Treatment Plant 49
Recovery of Priority Pollutants from Raw Wastewater from
Grit Chamber at South Burlington, NC Wastewater
Treatment Plant 50
Recovery of Priority Pollutants from Activated Sludge from
South Burlington, NC Wastewater Treatment Plant 51
Recovery of Priority Pollutants from Raw Wastewater from
Grit Chamber at Chapel Hill, NC Municipal Waste Treat-
ment Plant 52
Parts List for Aeration Tank Sampler 60
Operating Parameters for GG-MS-COMP System 63
Characteristics M/Z Ions Selected for Quantification of
Priority Pollutants 66
Estimated Limits of Detection for Selected Priority Pollu-
tants 68
Relative Molar Response Factors for Several Priority
Pollutants Using Selected M/Z Ions. . .• 70
Sampling Protocol for Municipal Treatment Facilities 73
Volatile Organics Identified in Airstream from Aeration
Basin (Plug Flow) at Durham, NC Plant 76
Analysis for Priority Pollutants in Air Stream from Grit
Chamber at South Burlington, NC Municipal Treatment Plant 78
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TABLES (cont'd.)
Number
24
25
26
27
28
29
30
31
32
33
34
35
36
Dl
D2
D3
D4
D5
D6
D7
D8
80
81
82
Estimation of Priority Pollutants Levels in Air Stream
From Aeration Basin at South Burlington, NC Munici-
pal Waste Treatment Plant
Estimation of Priority- Pollutants Emissions Rate from Aera-
tion of Activated Sludge at Durham, NC Treatment Plant .
Estimation of Priority Pollutants Levels in Vent from Pure
Oxygen (Closed Chamber) System at Danville, VA Municipal
Waste Treatment Plant.
Recovery of Priority Pollutants from Activated Sludge
(Durham, NC Plant) Using Designed Sampler. ........ 83
Quantity of Radiolabelled Priority Pollutants Used in Re-
covery Experiments 86
Parameters Used for Recovery Efficiency Studies of Priority
Pollutants, Simulating Municipal Treatment Facility
Operations ..90
Parameters Used for Determining Sampling Precision, Accuracy,
and "Memory Effect". „ . 92
Levels of Priority Pollutants Added to Air Stream from
Activated Sludge . . 94
Recovery of Radioisotopically Labelled Priority Pollutants
from Distilled Water, Raw Wastewater, and Sludge 95
Sampling Precision and Collection Efficiency for Selected
Priority Pollutants Using Tenax GC Sampling Cartridges . . 97
Sampling Accuracy for Selected Priority Pollutants Using
Tenax GC Sampling Cartridges 98
"Memory Effect" Contribution in Sampler Transfer Line from
Sampling Air Streams Containing Priority Pollutants. ... 99
Recovery of Priority Pollutants from Stored Tenax Sample
Cartridges •
Recovery of Priority Pollutants from Stored Tenax Sample
Cartridges ,,,..,... .172
Parts List for Aeration Tank Sampler. 175
Permeation Tubes for Several Volatile Priority Pollutants . . .181
Breakthrough Volumes for Several Priority Pollutants 186
Operating Parameters for GC-MS-COMP System ... 190
Characteristic M/Z Ions Selected for Quantification of
Priority Pollutants • -192
Chain of Custody Record 199
Examples of Previously Determined Relative Molar Response
Factors for Several Priority Pollutants Using Selective
M/Z Ions 20;L
,100
xx
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ACKNOWLEDGMENTS
The valuable assistance of Mr. J. Bunch, D. Newton, R. Williams, B.
Voss and J. Oxman for executing laboratory and field experimentation is
gratefully appreciated. GC/MS/COMP analysis was provided by Ms. D. Smith
and Mr. L. Kelner. The author wishes also to thank the personnel at the
Northside Durham Municipal Treatment Plant, Mason Farm Municipal Treatment
Plant, South Burlington Wastewater Treatment Plant and the Danville, VA
Facility.
The constant encouragement and helpful criticism of Messrs. H. 0. Wall
and Fred Bishop of the Municipal Environmental Research Laboratory, Environ-
mental Protection Agency, Cincinnati, OH are deeply appreciated.
xii
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SECTION 1
INTRODUCTION
ROLE OF AERATION IN WASTEWATER TREATMENT
Aeration, the transfer of air into liquid, has many applications in the
wastewater field. Aeration may occur naturally, for example at the air-
liquid interface between wastewater and the air above it, or it may be
induced, as by injection of air into the wastewater or by. mechanical agita-
tion of the wastewater to increase its exposure to the atmosphere. In
induced aeration, the gas phase may be provided directly from the atmosphere
(mechanical aeration), by compressed air (diffusion or injection aeration),
or by compressed oxygen (pure oxygen process).
Aeration is commonly used in biological wastewater treatment to provide
the oxygen needed by activated sludge organisms for aerobic decomposition
and to induce turbulence so that the sludge remains in suspension, in inti-
mate contact with food and oxygen. Forced aeration may also be used solely
for agitation. These applications will be described in greater detail
below.
Another application of aeration is in removing gases and other volatile
substances from water or wastewater. This application is generally utilized
for water treatment processes, such as removal of C02 before lime-soda
softening, removal of H2S, and removal of odor and taste producing substan-
ces secreted by microorganisms. A major application in the wastewater field
is air stripping of ammonia from domestic or industrial wastewaters.
The aeration systems examined during the course of this project were
designed to provide agitation alone (aerated grit chamber) or to provide
both oxygen and agitation (activated sludge). Removal of gases and volatiles
was not an objective. However, since the physical and chemical conditions
were appropriate for such gas transfer, it might be expected to occur.
TYPES OF REACTORS EMPLOYED IN WASTEWATER TREATMENT
The principal reactor types used in wastewater treatment are (1) plug
flow reactor, (2) complete-mix reactor, and (3) arbitrary flow reactor (1).
In plug flow, aliquots of wastewater enter the tank, pass through it, and
are discharged in the same sequence in which they enter. Each aliquot
retains its identity and each remains in the tank for the same length of
time. In a treatment system utilizing plug flow, one would expect the
concentration of wastewater components to be highest at the influent (input)
end and lowest at the effluent (exit) end. Plug flow reactors are generally
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long tanks with a high length:width ratio. In complete mix reactors, incom-
ing aliquots are almost immediately dispersed throughout the tank. The
concentration of wastewater components would be approximately the same at
any point within the reactor. To facilitate complete mixing, the reactors
are generally round or square.
In practice, ideal plug-flow or complete mix rarely occurs. Despite
design of the reactors, some degree of partial mixing occurs, resulting in
something intermediate between the two. This is designated "arbitrary
flow."
AIR INTRODUCTION DEVICES
A wide variety of aeration devices is available (1-3). The two major
categories applicable to induced (forced) aeration of wastewaters are (1)
subsurface diffusers and (2) mechanical aerators.
In the first category, compressed air (or oxygen) is introduced into
the tank by means of coarse-bubble (nozzles, spargers) or fine-bubble
(porous plates and tubes) devices. While fine bubbles are theoretically
more efficient for gas transfer, in practice they tend to clog easily and to
enhance foaming. Compressed air may be introduced at or near the bottom, or
at one side to encourage spiral movement.
In mechanical aerators, the objective is to put the wastewater into
greater contact with the atmosphere. This can be accomplished by surface
paddles, submerged paddles, partially submerged rotating brushes, propeller
blades so located as to aspirate air down into the water, turbine blades
which draw the wastewater up and spray it over the surface, or other devices
(4).
APPLICATIONS OF AERATION
Aeration may be employed in wastewater treatment for agitation and/or
oxygen transfer, depending on the objective of the unit process.
Aerated Grit Chamber
Wastewater often contains sand, cinders, gravel, fruit pits, and other
inert heavy particles which might damage pumps and other mechanical equip-
ment, create deposits in pipes and channels, and accumulate in the digester.
Therefore, grit removal is generally one of the first processes applied to
wastewater, being preceded only by coarse (bar) screening and/or comminu-
tion. Ideally, grit chambers should remove only heavy inorganic materials,
leaving the organics to be degraded in subsequent treatment. In the con-
ventional grit chamber, still in use at most wastewater treatment plants,
the grit chamber relies on gravity and slightly reduced flow rate (^1 fps
or 0.3 m/s) to remove particles with a specific gravity of 2.65 and diameter
of 2 x 10~2 cm (3,4). Because some organic material is also deposited, the
collected grit may have to be washed before disposal. Since grit removal is
performed at the point at which the wastewater is at its maximum strength,
septic conditions accompanied by odor production are common in grit chambers.
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The aerated grit chamber was designed to accomplish a higher degree of
grit removal, to reduce odors, and to wash the organic material from the
grit. The most effective aerated grit chambers induce a spiral flow by
injecting air 18-24 inches above the bottom along one side of the?chamber
(1). Detention time of the wastewater is ^3 min. Since aeration occurs at
the point of maximum wastewater strength, substantial transfer of gases and
volatiles might be expected to occur. In practice these systems require
careful adjustment of air velocity to ensure removal of the grit without
sedimentation of the lighter organic particles. A representative air
velocity is 5 cfm of air per foot of tank length (1).
Biological Processes
Primary treatment of municipal domestic wastewater is generally accom-
plished by physical processes such as gravity sedimentation and flotation.
Dissolved and finely divided materials are not removed in these processes.
Biological (secondary) wastewater treatment is designed to remove pollutants
from wastewater by sorption to biological films (as in trickling filters) or
to biological floe (as in activated sludge).
In the activated sludge process, nonsettleable substances are converted
into biological floe (sludge) which can be removed by sedimentation, or into
stable, mineralized endproducts which have a lower oxygen demand. This
process is most commonly conducted in complete mix reactors with forced
aeration systems, although many variations exist. The process is dependent
on bringing a large concentration of active organisms (mixed liquor suspended
solids of about 2500 mg/£) into intimate contact with food (organics) and
oxygen. Aeration provides the desired turbulence and oxygenation-.
To provide the sludge with adequate oxygen, it is generally agreed that
at least 0.5 mg/Ji, of dissolved oxygen (DO) should be present at all times in
all parts of the aeration tank.
In conventional activated sludge plants, aeration is accomplished with
air. For municipal wastewater, air.requirements are about 0.8 - 1.5 ft3 per
gal of wastewater. However, aeration requirements vary according to strength
of the wastewater, and estimation of air requirements is based preferably on
the biochemical oxygen demand (BOD), being about 1000 ft3 of air per pound
of BOD in the influent wastewater. Regardless of strength, a minimum air
flow of ^3 cfm/ft of tank length must be provided to prevent settling.
Conventional activated sludge systems, especially those located in warm
or temperate climates, are generally open to the atmosphere.
The maximum dissolved oxygen concentration which can be obtained with
air aeration is limited by the partial pressure of.the oxygen in the air.
Higher DO concentrations can be obtained if pure oxygen is used in aeration.
After development of cost-effective on—site oxygen production processes, the
pure oxygen activated sludge process came into use in the early 1970's.
In this system high purity oxygen is injected into aeration tanks and is
quickly dispersed with mixers, allowing rapid and efficient gas transfer.
Since higher concentrations of activated sludge can be maintained^', the
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required detention time can be reduced. Because of this, the oxygen process
is frequently adopted to upgrade and increase the capacity of existing
activated sludge plants. To assure most cost-effective use of the oxygen,
pure oxygen activated sludge tanks are covered and the oxygen is recircula-
ted. The complete mix reactor is generally used, but the process can also
be applied to overloaded plug-flow systems (1).
DESCRIPTION OF LOCAL MUNICIPAL TREATMENT FACILITIES
Testing was conducted at municipal wastewater treatment plants in
North Carolina and Virginia. Plants were selected on the basis of (1) type
of aeration and (2) proximity to Research Triangle Institute.
Mason Farm Wastewater Treatment Plant, Chapel Hill, NC
The Mason Farm Wastewater Treatment plant treats wastewater from the
towns of Chapel Hill and Carrboro. There is essentially no industry in the
area, and extensive records kept by the Town of Chapel Hill and the UNC
Wastewater Research Center characterize the wastewater as a "typical domes-
tic sewage." A flow diagram of the plant is shown in Figure 1. Typical
flow is 4.8-5 mgd. The plant is noteworthy because of the dual, identical
treatment trains in the older part of the plant. Units include:
(1) Mechanical bar screen
(2) Conventional grit chamber
(3) Primary settling basins
(4) Alum injection for phosphate removal
(5) High rate trickling filters
(6) Intermediate settling basins
(7) Activated-sludge type nitrification system
(8) Final settling basins
(9) Chlorination chamber
(10) Two-stage anaerobic digesters.
Samples for this project were taken over the conventional grit chamber.
Northside Treatment Plant, Durham, NC
The Northside Treatment Plant treats wastewater from homes, businesses,
and industries in the northeast side of Durham. Typical flow is 6.3 mgd.
A diagram of the plant is shown in Figure 2. Units include:
(1) Coarse screening (mechanical bar screen)
(2) Grit removal and flotation of grease in a vacuum process
(Vacuator)
(3) Roughing trickling filtration
(4) Primary sedimentation
(5) Conventional activated sludge with 6-8 hr detention and forced
air diffusion (observation of the tanks indicates that the flow
pattern is arbitrary, somewhere between plug flow and complete
mix)
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(6) Secondary sedimentation with sludge recycle
(7) Chlorination
(8) Anaerobic sludge digestion
This plant was used for preliminary experiments required for design of the
sampling system. Samples were taken at the influent end of the aeration
tanks. These tanks are each 15 x 200 ft with a depth of 13 ft. Liquid
depth is 'VLl.S ft. Air is injected into each tank by 344 porous plates, 12
x 12 in., set vertically in double rows in a header placed 12 in. above tank
bottom.
Northside Facility, City of Danville, VA
The Northside Plant treats domestic and industrial wastewater from the
City of Danville. Unit processes include:
(1) Screening
(2) Grit removal
(3) Preaeration and grease floatation
(4) Primary sedimentation
(5) Pure oxygen activated sludge
(6) Secondary sedimentation
(7) Disinfection
A diagram of the plant is shown in Figure 3. The facility, completed in
1976, serves a population of ^50,000 and treats municipal and industrial
wastewater. The plant has a nominal flow capacity of 24 mgd and is currently
treating ^18 mgd. Approximately 60% of the flow comes from industries,
including textile manufacturing, rubber manufacturing, glass manufacturing,
and tobacco products. The plant utilizes the Unox process (Union Carbide).
Oxygen is produced on-site by the pressurized swing adsorption (PSA) process.
The pure oxygen aeration chamber is completely enclosed and is operated
under pressure. The pressurized oxygen feeds into the chamber above the
liquid surface. Agitation and oxygenation are accomplished by mixers
located just below the surface and just above the bottom. The system is
vented through a stack above the aeration chamber. For this project, a
sample was taken of the vent gas.
South Burlington Plant, Burlington, NC
The South Burlington Plant treats municipal and industrial wastewater
from the southern half of Burlington, NC. The average flow is,^5.5-6.0 mgd,
^35-40% of which is industrial. The population equivalent is ^28,000. The
major organic load comes from the. textile industries in the area. This
plant has an aerated grit chamber, but the aeration is used only infre-
quently due to operational difficulties in adjusting the air flow. Air is
provided by coarse tube-type diffusers. Secondary treatment is provided by
conventional activated sludge with a nominal 8 hr detention period. Air in
the influent end of the 4 tanks is provided through plastic nozzles located
about 1 ft above the bottom of the tank. At the other end. of each tank,
mechanical aerators of the updraft type provide aeration and agitation.
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At this plant, samples were taken above the aerated grit chamber
(while the aeration system was in operation) and above the influent end of
the AS aeration tanks.
-------
SECTION 2
CONCLUSIONS
Volatile priority pollutants were concentrated from air streams passing
through wastewaters on Tenax GC sorbent in a short glass tube. Recovery of
the volatile priority pollutants was accomplished by thermal desorption,
purging with He into a liquid-nitrogen cooled nickel capillary trap, and
introducing the vapors into a gas chromatographic column where the vapors
are separated from each other. Characterization and quantification of the
priority pollutants were accomplished by mass spectrometry using mass frag-
mentography.
The linear dynamic range for analysis of priority pollutants depended
upon two principal phenomena. The first was a function of breakthrough
volume for each pollutant trapped on the Tenax GC sampling cartridge and the
second was related to the inherent sensitivity of the mass spectrometer for
each organic compound. Thus the range and sensitivity varied considerably
from one priority pollutant to another. The linear range for the quantita-
tion on a gas chromatograph/mass spectrometer/computer (GC/MS/COMP) was
generally three orders of magnitude and was principally dependent upon the
linearity of the A/D converter (interface) of the GC/MS computer system.
At the present time there are no known potential interferences to quan-
tification using the developed collection and analysis system. The use of a
specified, packed, glass chromatographic column in combination with selective
ion chromatography provide sufficient specificity for the analysis of vola-
tile priority pollutants.
The accuracy and reproducibility of this method was +10% to +30% as
determined by the relative standard deviation for the different substances
when replicate sampling cartridges were examined. The inherent analytical
error was a function of several factors: (1) ability to accurately deter-
mine the breakthrough volume for each of the identified organics; (2) the
accurate measurement of the volume of the air stream sampled; (3) the per-
cent recovery of the organic priority pollutant from the sampling cartridge
after storing; (4) the reproducibility of thermally desorbing compounds from
the Tenax cartridge and their introduction into the analytical system; (5)
the accuracy achieved in determining the relative molar response ratios
between the identified substance (priority pollutant) and the external
standards (perfluorobenzene and perfluorotoluene) used for calibrating the
analytical system; (6) the reproducibility achieved in transmitting the
sample through a gas chromatographic column and (7) the day-to-day reliabi-
lity of the MS/COMP system.
10
-------
The accuracy of the analysis for Tenax cartridges containing priority
pollutant was generally +30%.
GC/MS analysis was extremely sensitive and specific for volatile
priority pollutants in air streams from wastewaters of municipal wastewater
treatment plants. The sensitivity was generally between 1-10 ng/A of air.
The combination of the gas chromatographic column and the selection of
specific or unique ions (representing the various compounds of interest
identified in the samples) yielded a relatively specific assay for these
priority pollutants.
Because some of the compounds of interest may be hazardous to man, it
is extremely important to exercise safety precautions in the preparation and
disposal of liquid and gas standards, cleaning of used glassware, etc.
11
-------
SECTION 3
RECOMMENDATIONS
Several major research tasks should be expanded and pursued: (1) fur-
ther research should be conducted on the storage of field samples containing
priority pollutants on Tenax GC cartridges in order to precisely define the
expected recoveries; (2) The accuracy of sampling should be determined by
spiking the air streams from the wastewaters with known amounts of priority
pollutants to determine whether the substances are accurately collected;
(3) Since the capacity of a Tenax GC sampling cartridge might be exceeded
by the total pollutant load in the sample, displacement chromatography
experiments need to be performed; (4) The efficiency in transferring pollu-
tants emitted from air streams to the sampling manifold via the umbilical
cord should be further evaluated and (5) The design of the sampling head
should be perfected for convenient use at aeration ponds and grit chambers.
12
-------
SECTION 4
PROGRAM OBJECTIVES
The objectives of this research program were to develop procedures to
representatively sample air streams passing through wastewaters in grit
chambers and aeration basins at municipal wastewater treatment facilities
and to analyze representative samples for volatile toxic organic pollu-
tants .
The specific aim was to evaluate three types of aeration systems in
order to develop the required sampling procedures. The types of aeration
systems examined were: (1) pure oxygen [closed chamber]; (2) totally mixed
activated sludge basin and (3) plug-flow basins. The method employed a trap
and inject approach for quantification using gas chromatography/mass
spectrometry/computer.
The purpose of the program was also to establish the accuracy, preci-
sion and sensitivity of the analytical procedures developed by adding known
quantities of at least 25 of the. toxic organics (priority pollutants) to
wastewater in laboratory or pilot vessels simulating the aeration processes
in wastewater plan'ts. Using the developed and evaluated procedures, the
final aim was to apply the methodology to the analysis for priority pollu-
tants in air streams passing through wastewater at several municipal plants.
13
-------
SECTION 5
EVALUATION OF TENAX GC SAMPLING CARTRIDGES FOR USE WITH
PRIORITY POLLUTANTS
INTRODUCTION
In order to quantitatively collect volatile priority pollutants from
air streams passing through wastewaters onto a solid sorbent such as Tenax
GC, several facets of the technique need to be evaluated. The collection
of priority pollutants on a sampling cartridge, followed by thermal desorp-
tion and GC with mass spectrometric detection, permits the sensitive detec-
tion and quantification of adsorbable vapors.
When polluted gas enters a sorbent bed such as occurs during air
sampling, an .equilibrium zone is established near the point of entry which,
as more pollutant vapor is introduced, may expand through the packing
length until the capacity of the sorbent is exceeded. Also, if after an
initial period of time, additional polluted vapors are introduced, then as
the purging of the packing bed continues, the zones of vapors will move
through the packing bed. When the zones reach the end of the available
packing bed and the vapors begin to leave, breakthrough has occurred. Thus
breakthrough volume is simply the elution volume (Ve) which can be calcu"-
lated if the time required for the zone to migrate and elute from the
sorbent bed and the sampling rate are known. In an ideal collection system,
breakthrough volume has an infinite value at ambient temperature. The
relationship which describes the amount of vapor adsorbed to a given quantity
of adsorbent as a function of pressure, temperature and concentration of
the solute vapor is given by the Langmuir equation which has been previously
discussed (5,6). The breakthrough volumes for a series of representative
volatile (purgeable) priority pollutants were determined.
Since the humidity of the air streams passing through wastewaters will
reach essentially 100%, the trapping of residual amounts of water vapor on
Tenax GC will occur. Thus, the effect of the residual water on recovering
priority pollutants needed evaluation. Also, water vapor might affect the
efficient transfer of organic vapors from the sampling device to the analy-
tical column.
Finally, recovery of priority pollutants from the sorbent as a func-
tion of storage time needed study since immediate analysis is not always
possible.
This section examines the potential problems associated with (1)
breakthrough volume, (2) recovery of priority pollutants from the collection
14
-------
device as a function of storage time, and (3) the effect of drying sampling
cartridges with calcium sulfate prior to their analysis.
EXPERIMENTAL
Determination of Breakthrough Volumes
Breakthrough volumes were estimated for a number of "purgeable" prio-
rity pollutants. Determining the elution volume for the priority pollutant
on a gas chromatographic column packed with the sorbent, Tenax GC, was the
method of choice (6,7,8). A 3 mm-i.d. x 3.05-m stainless steel column was
used. After injecting each vapor mixture, the elution volume was deter-
mined for each of the individual compounds as the product of flow rate and
elution time. A series of injections was made at decreasing temperatures
and a plot of the log 1/v vs. temperature was constructed. Using linear
regression analysis, the Breakthrough volumes (50% loss) at several ambient
temperatures were determined by extrapolation. The standard cartridge
dimensions employed in the field are 1.5-cm i.d. x 6.0-cm bed length.
This technique for determining breakthrough volumes has been compared
with other techniques and is considered a viable rapid approach for the
determination of breakthrough volumes (5-8).
Preparation of Tenax GC Sampling Cartridges
All glassware, sampling tubes (Pyrex glass, 1.5 cm i.d. x 10 cm in
length), cartridge holders (Kimax © ), etc. , were washed in Isoclean/water,
rinsed with deionized-distilled water then acetone, and air-dried. Glassware
was heated to 450-500°C for 2 hr to insure that all organic material was
removed prior to its use.
Virgin Tenax GC was extracted in a Soxhlet apparatus for a minimum of
18 hrs, eachj with pentane and methanol (10). The Tenax GC sorbent (Applied
Science, State College, PA) was dried in a dry-box with nitrogen purging to
remove excess solvent and then was dried further in a vacuum oven at 100°C
for 3-5 hrs. All operations hereafter must be carried put in a room free
of organic vapors from laboratories, etc. Tenax GC was sieved to provide a
fraction corresponding to 35/60 mesh. This fraction was used for preparing
sampling cartridges throughout,the study. In those cases where sampling
cartridges of Tenax GC were recycled, the adsorbent was again extracted
in a Soxhlet apparatus with methanol as described for the virgin material,
as well as with a non-polar solvent, n-pentane, in order to remove the rela-
tively non-polar and nonvolatile materials which may have accumulated on
the sorbent bed during previous uses.
Tenax GC cartridge samplers were then prepared (10-cm long x 1.5-cm
i.d. glass tubes containing 6.0-cm sorbent anchlored with glass wool plugs)
arid conditioned at 270°C with helium flow at 30 ml/min for 1 hr. The
conditioned cartridges were transferred to Kimax © (2.5 cm x 157 cm) culture
15
-------
tubes; immediately sealed using TefIon\S/inserts in aluminum lined caps,
and cooled (8-10). The Kimax® containers were placed in a metal-sealable
can (e.g., paint can) to minimize contamination. Cartridges prepared in
this manner retained a low "background" of organics for a period of six
weeks.
Gas-Liquid Chromatography
Gas-liquid Chromatography (GC) was conducted on a Varian 3700 series
gas chromatograph (Varian Instr. Inc., Walnut Creek, CA) equipped with dual
flame ionization detectors. A previously described thermal desorption unit
(Figs. 4,5) was used for transferring adsorbed vapors from the Tenax GC
sampling cartridges to the analytical column (11,12). The analytical
column was a 100-m,glass support-coated open-tubular (SCOT) capillary
coated with OV-101 stationary phase. The SCOT column was programmed from
30°C to 240°C at 4°/min. Carrier gas (helium), hydrogen and air flows were
3, 30, and 200 ml/min, respectively. The detector temperature was main-
tained at 250°C.
Table 1 presents the operating parameters for the thermal desorption
unit and the GC.
Calibration Techniques
For the purpose of calibrating instruments for quantitative evaluation
studies of priority pollutants throughout this program, it was necessary to
accurately spike Tenax GC sampling cartridges with known amounts of prio-
rity pollutants and the internal standards, perfluorobenzene and perfluoro-
toluene. Figure 6 depicts the permeation system which was used for accura-
tely delivering known concentrations of air/vapor mixtures to the Tenax GC
cartridges. The performance of this permeation system has previously been
described (9,13).
Table 2 provides a list of the priority pollutants, the materials used
for constructing permeation tubes and the permeation rates which were es-
tablished by gravimetric means (9,13).
Data Analysis
The gas-liquid chromatograph was calibrated by analyzing a series of
Tenax GC cartridges which were loaded with known amounts of priority pol-
lutants from the permeation system. For the purpose of determining the
percent recoveries and subsequent studies, the response of the gas chroma-
tograph to each of the priority pollutants was used in order to determine
the quantity of the priority pollutant for each experimental condition.
Either peak height or area was used for quantification. Varian CDS-11 and
Spectra-Physics integrators were used for determining peak areas.
Storage Studies
Tenax GC sampling cartridges (1.5-cm i.d. x 6.0-cm bed length) were
loaded with calibrated amounts (400-800 ng/cartridge) of priority pollutants
16
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0.04 in. id x 0.062 in.od x 36 in.
Ni capillary
Thermocouple
1/16 in. Swagelock union
h"
6cm
Figure 5. Cryo-heater module for inlet-manifold (12).
18
-------
TABLE 1. PARAMETERS FOR INLET-MANIFOLD AND GAS-LIQUID CHROMATOGRAPHY
Parameter
Condition
Inlet-manifold
desorption chamber and valve
capillary trap - trap cycle
inj ect cycle
thermal desorption time
He purge rate
GLC
column (100-m OV-1Q1 SCOT)
He carrier flow
FID temperature
270°C
-195°C
+250°C
8 min
15 ml/min
30-240°C at 4°C/min
3.0 ml/min
250°C
19
-------
TEFLON-PLUG
STOPCOCKS
NEEDLE VALVES
MIXING CHAMBER
PERMEATION CHAMBER
JACKET
THERMOSTAT, HEATER , AND
CIRCULATING PUMP
CARRIER GAS LINES
THERMOSTAT FLUID LINES
Figure 6. Permeation system for generating air/vapor mixtures (9,13)
20
-------
TABLE 2. PERMEATION TUBES FOR SEVERAL VOLATILE PRIORITY POLLUTANTS
Priority pollutant
methyl choride
dichlorodifluoromethane
methylbromide
vinyl chloride
chloroethane
dichlorome thane
• trichlorof luoromethane
1, 1-dichloroethylene
1, 1-dichloroethane
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
bis-(chloromethyl) ether
1 , 2-dichloropropane
1 , 3-trans— dichloropropane
trichloroethylene
dibromochloromethane
1, 3-cis-dichloropropene
1,1, 2-trichloroethane
benzene
2-chloroethylvinyl ether
bromoform
1,1,2, 2-tetrachloroethene
1,1,2, 2-tetrachloroethane
toluene
chlorobenzene
ethyl benzene
acrolein
acrylonitrile
bis- (2-chloroethyl) ether
perfluorotoluene
1 , 3-dichlorobenzene
per f luor obenz ene
Permeation tube
Dimensions
(O.D. x I.D. x length, cm)
0.64 x 0.48 x 6.5
Unknown
0.64 x 0.48 x 6.0
0.64 x 0.48 x 10.0
Unknown
0.64 x 0.48 x 11.0
Unknown
0.64 x 0.48 x 10.1
0.64 x 0.48 x 9.9
0.64 x 0.48 x 10.0
0.64 x 0.48 x 11.0
0.64 x 0.48 x 8.0
0.64 x 0.48 x 8.0
0.64 x 0.48 x 9.9
0.64 x 0.48 x 5.2
Unknown
0.64 x 0.48 x 7.7
Unknown
0.64 x 0.48 x 10.0
Unknown
Unknown
0.64 x 0.48 x 10.3
0.64 x 0.32 x 0.6
Unknown
0.64 x 0.48 x 5.1
0.64 x 0.48 x 5.2
0.64 x 0.32 x 7.0
0.64 x 0.48 x 7.0
0.64 x 0.48 x 5.5
0.64 x 0.48 x 12.7
0.64 x 0.48 x 10.0
0.64 x 0.48 x 10.4
0.64 x 0.48 x 8.3
0.64 x 0.48 x 7.2
0.64 x 0.32 x 9.0
0.64 x 0.48 x 5.5
Material
FEP
FEP
FEP
FEP
TFE
TFE
TFE
FEP
TFE
TFE
TFE
TFE
TFE
TFE
TFE
PE
PE
TFE
PE
TFE
TFE
TFE
TFE
TFE
TFE
FEP
PE
FEP
Approximate rate
g/min
1.8 x 10~6
1.2 x 10~6
2.0 x 10~6
7.0 x 10~7
1.0 x 10~6
4.2 x 10~7
1.1 x 10~5
6.4 x 10~8
4.0 x 10~7
9.1 x 10~8
3.0 x 10~8
1.1 x 10~7
9.8 x 10~8
2.2 x 10~6
6.2 x 10~8
7.1 x 10~6
2.5 x 10~5
3.6 x 10~7
9.7 x 10~6
1.9 x 10~7
2.0 x 10~7
6.8 x 10~8
1.3 x 10~6
1.0 x 10~6
1.0 x ID'10
8.94 x 10~6
1.1 x 10~7
8.5 x 10~6
21
-------
from the permeation system. The Tenax GC cartridges were then analyzed
immediately, as well as at 14 and 21 days, respectively, using thermal
desorption gas-liquid chromatography with flame ionization.
Sample Desiccation
Tenax GC sampling cartridges were loaded with calibrated amounts (400-
800 ng/cartridge) of a selected series of priority (purgeable) pollutants
and then exposed to a humid atmosphere which was generated by purging a
vessel containing water at 40°C. Purging of the Tenax cartridge with humid
atmosphere was at 25 ml/min for 5 min.
Tenax GC sampling cartridges which had and had not been exposed to
humid atmospheres were analyzed immediately (5 min after humidification)
and at 2 hrs, 2, and 3 weeks of storage. In each case, the Tenax GC samp-
ling cartridge was placed in a Kimax ® culture tube (Fig. 7) which con-
tained approximately 1 gram of CaSOij. The calcium sulfate had previously
been heated in a muffle furnace to 500°C for approximately .4 hr to insure
that the calcium sulfate was anhydrous and free of organic volatiles.
All experiments were conducted in duplicate. Tenax sampling cartridges
were analyzed by gas-liquid chromatography with flame ionization detection
as described .above.
RESULTS AND DISCUSSION
Breakthrough Volumes
Table 3 presents the breakthrough volumes for several priority (purge-
able) pollutants. The priority pollutants are arranged according to boil-
ing point and divided into halogenated and non-halogenated groups. These
data indicate that the boiling point does not always determine the break-
through volume. For example, the breakthrough volume of 1,2-trans-dichloro-
ethylene (1.9 A/cartridge) which has a boiling point of 47.5°C is less than
that of dichloromethane (14 H/cartridge). Furthermore, the halogen substi-
tution pattern plays an important role in determining the retention volume
on Tenax GC sorbent. The presence of an aromatic substituent also greatly
increases the breakthrough volume [compare halogenated compounds with
similar boiling points (e._g_., chlorobenzene vs_. 1,1, 2,2-tetrachloroethane) ].
These data are important for quantitative sampling of air streams.
Quantitative data may be obtained for 1,1-dichloroethylene if the sampling
volume is less than the breakthrough volume. For example, to estimate the
concentration of 1,1,-dichloroethylene in the air stream from the waste-
water systems at an ambient temperature of 32.2°C (90°F), a sampling volume
of 1 & or less should be taken. This volume (as demonstrated in Section 9)
is the desired volume that is required to collect a sufficient quantity of
priority pollutant for ppb analysis, while not exceeding the background
threshold (resolution requirement) or saturating the instrumental analysis
systems.
22
-------
-P/ieno/f'c cap with 1~FE
lineal st'/tcone seal
320-3-302
^•21 cm g/ass
320-3- 301
-1.3cm, TFEspacer
320-3-303
1 •---•-
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G.C. Cartridge, 3£0-3-iOi
Figure 7. Sampler cartridge transport tube (Nutech Corp.,
Durham, NC).
23
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The data presented in Table 3 serve as a guideline for selecting the
volume which may be sampled at various ambient air temperatures if one
wishes to achieve quantitative estimation of priority pollutants.
Sample Storage
Table 4 presents the recovery of priority pollutants from Tenax GC
sampling cartridges which were stored for 14 and 21 day periods. These
data represent recovery from Tenax sampling cartridges which were loaded
with calibrated amounts of priority pollutants under ideal conditions,
jL.je., in the absence of humidity. As these data indicate, most compounds
may be stored adsorbed to Tenax GC for as long as 3 weeks prior to analysis.
However, it is recommended that the sampling cartridges be analyzed as soon
,as possible after sampling has been completed.
Effect of Calcium Sulfate Drying on Recovery of Priority Pollutants from
Tenax GC Cartridges
Tables 5, and 6 present the relative recoveries of priority pollutants
from Tenax GC cartridges which were humidified and stored for various
lengths of time in the presence of CaSO^ to determine the effects of drying
on the percent recovery of priority pollutants. It is apparent that, in
some cases, the drying step enhances the recovery of the priority pollu-
tants while in other cases some losses are observed. However for the
majority of compounds listed, "drying" in the presence of CaSO, decreases
their percent recoveries.
25
-------
TABLE 4. RECOVERY OF PRIORITY POLLUTANTS FROM STORED TENAX CARTRIDGES
Priority pollutant
1, 1-dichloro ethyl ene
1, 2-trans-dichloroethylene
1,1, 1-trichloroethane
1, 2-dichloroethane
trichloroethylene
1, 2-dichloropropane
tetrachloroethylene
chlorob enz ene
bis- (2-chloroethyl) ether
bis- (chloromethyl) ether
acrolein
acrylonitrile
benzene
toluene
ethylbenzene
chlorobenzene
1, 1-dichloroethane
bromodichloromethane
bromoform
Percent
14 days
48 + 12
73+9
92 + 2
100 + 7
99 + 9
86 + 4
97 + 3
80+7
86 + 6
41+4
45 + 15
ND
104 + 8
103 + 3
61+9
80+7
102
106
79
recovery
21 days
35 + 8
99 + 12
NDa
122 + 9
87 + 13
ND
68 + 3
87 + 3
93
ND
49 + 6
81 + 6
104
103 + 7
65 + 11
80 + 4
90
77
ND
ND = not determined.
26
-------
TABLE 5. RELATIVE RECOVERIES OF WET VS. DRIED SAMPLES USING
CaSO, FOR 2 HR
Priority pollutant
benzene
bromodichloromethane
toluene
chlorobenzene
1, 2-dichlorobenzene
1 , 1-dichloroethylene
1, 2-trans-dichloroethylene
chloroform
ethylene dichloride
1, 2-dichloropropane
1,1, 2-trichloroethane
tetrachloroethylene
ethylbenzene
1,1,2, 2- tetracb.loroetb.ane
bis- (2-chloroethyl) ether
1, 3-dichlorobenzene
acrolein
acrylonitrile
trichloroethylene
Humidified
15.4 + 2.1
1.6 + 0.3
49.9
25.9 +2.9
37.9 + 24.1
17.3
8.3 + 1.8
2.6 + 0.5
6.6 + 0.4
7.6 + 1.1
16.4 + 1.8
6.8 + 0.5
18.5 + 1.6
16.3 + 5.3
2.6 + 0.4
30.7 +0.6
23.8 + 0.3
15.2 + 2.5
39:2 +3.9
Humidified, dried
13.7+1.3
1.5 + 0
53.8 + 0.8
31.3 +1.1
37.9 + 16.4
25.8
6.0
1.9 + 0.1
3.5 + 0
4.7 + 0.3
8.5 + 1.5
4.6 + 0.6
11.6 + 1.6
8.3 + 1.5
0.85 + 0.3
21.7 +5.7
24.7 +1.7
15.7 + 0.7
36.7 +3.9
% D/H
89
94
110
120
100
149
72
73
53
62
52
68
63
51
33
70
103
102
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SECTION 6
RECOVERY OF "PURGEABLE" PRIORITY POLLUTANTS FROM AQUEOUS MEDIA
INTRODUCTION -
It would be desirable if the levels of priority pollutants which are
determined in the air stream passing from wastewaters could be related to
their concentration in the original raw or municipal wastewater. Some pre-
liminary studies have been performed in estimating the potential concentra-
tions of priority pollutants which might be found in the air passing through
water (14). These studies have considered the mass transfer of vapors
between two phases and the Henry's law constant. Using these relationships,
calculations have been performed for chloroform as the model compound (14).
However, one of the important assumptions of this approach is that the
priority pollutants behave as ideal compounds which is necessary when
applying Henry's law. One of the factors not taken into consideration in
these calculations was the possiblity that the priority pollutants might be
adsorbed to the solid phase particles and thus not available for stripping
by the air stream.
In order to examine the possibility of whether Henry's law can be
applied, a series of experiments was conducted to determine the percent
recovery of priority pollutants from distilled water and from raw and
municipal wastewater. Comparison of these data would allow the analyst then
to ascertain whether an empirical approach is feasible.
EXPERIMENTAL
Distilled Water Experiments
Three vessel configurations were used in the recovery studies of
priority pollutants from distilled water (Fig. 8). The first two vessels
(Fig. 8) permitted the water to be circulated in a manner similar to aera-
tion ponds at municipal treatment plants. Air was passed through the column
of water producing a circular vector motion in the vessel. Two vessels of
this design were employed; the basic differences were in their diameter to
length ratios. A'third vessel (Fig. 8) was also used; however, in this case
a sintered glass frit created a fine bubble dispersion of the air stream as
it passed into the liquid column.
Standard solutions of the priority pollutants were prepared in methanol
and added to distilled water to produce the desired final concentrations.
In all cases, the experiments were conducted in duplicate.
29
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Purging of the air stream through the three vessel types (Fig. 8) was
conducted using an air/liquid volume ratio of 2:-l. The rate was 80 ml/min.
For purposes of comparison, a constant volume (400 ml) was used in all
experiments. The air stream passed through a Tenax GC sampling cartridge
(1.5 cm x 6.0 cm) which was identical to that used in field experiments.
Analysis of these cartridges was performed as described in Section 5 under
gas-liquid chromatography.
Methods-of-Addition Studies
Methods-of-addition studies were performed with activated sludge mixed
liquor. Increasing measured amounts of priority pollutants were added
followed by purging, trapping, and GC/fid analysis. Standard solutions of
the priority pollutants were prepared in methanol and added directly to the
mixed liquor. An equilibration time of 30 min was used prior to beginning
the purge and trap for the priority pollutants.
The purging experiments employed the vessel (Fig. 8) with a glass frit
to produce a fine air bubble stream. Four-hundred-mi volumes of mixed
liquor were purged in all cases.
Activated sludge from the Durham, NC, Northside Sewage Treatment Plant
was used. The experiments were performed at the treatment plant using fresh
sludge, since its transport back to the laboratory might have changed the
integrity of the sample. Also, for these reasons a short equilibration time
was used.
Using 400 ml of activated sludge mixed liquor spiked with varying
amounts of priority pollutants, the sample was purged with 800 ml of air at
80 ml/min. The priority pollutants were trapped on a Tenax GC sampling
cartridge (1.5-cm i.d. x 6.0-cm bed length) and then analyzed by GC/fid as
described under Section 5.
Recovery Studies on Raw Wastewater and Activated Sludge Mixed Liquor
Standards of each priority pollutant were prepared in methanol and
added to raw wastewater and activated sludge mixed liquor to produce a final
concentration of 'vl ppb. Vessel configuration No. 3 was used (Fig. 8).
Again 800 ml of air was passed through 400 ml wastewater at 80 ml/min. The
purge-and-trap technique was identical to that described for the methods of
addition experiment. The priority pollutants were collected onto Tenax GC
sampling cartridges and analyzed by GC/MS/COMP techniques. All experiments
were conducted in triplicate.
Gas Chromatography/Mass Spectrometer/Computer Analysis
A previously described inlet manifold was used for thermally recovering
priority pollutants trapped on Tenax GC sampling cartridges and transferring
them to a gas chromatograph/mass spectrometer/computer system (5,6,8,9,10,12),
This manifold was designed to be used with either packed or support coated
open tubular (SCOT) columns if necessary.
31
-------
A Finnigan Model 3300 GC/MS system equipped with a PDP-12 computer was
capable of providing ion chromatograms as well as reporting the absolute
intensity or areas of ion peaks. Quantitative data concerning the priority
pollutants of interest were based on a ratio of responses between compounds
and internal standards. The instrumental conditions used for the analysis
of priority pollutants collected on the sorbent Tenax GC sampling cartriges
is given in Table 7. The thermal desorption chamber and the six-port Valco
valve (Valco Instr., Inc., Houston, TX) were maintained at 270°C. The glass
jet separator was maintained at 250°C. The mass spectrometer was set to
scan the mass range from 25-300 amu. The helium purge gas through the
desorption chamber was adjusted to 15 ml/min. The nickel capillary trap on
the inlet manifold was cooled with'liquid N£. In a typical thermal desorp-
tion cycle, a sampling cartridge was placed in the preheated desorption
chamber and the helium gas was passed through the cartridge to purge the
priority pollutant vapors into the liquid nitrogen capillary trap ,[the inert
activity of the trap has been shown in previous studies (9)]. After the
desorption was completed, the six-port valve was rotated and the temperature
on the capillary loop was raised rapidly (>150°/min). The carrier gas
introduced the vapors onto the gas chromatographic column, the gas chroma-
tographic column was held for 3 min at 60°C and then programmed 8°/min to
160°G and held until all compounds were eluted.
A stainless steel tube (8 ft in length x 0.1-in. i.d.) packed with
Carbopack C (60/80 mesh) coated with 0.2% Carbowax 1500 preceded by a 1-ft
x 0.1-in. i.d. column packed with Chromsorb W coated with 3% Carbowax 1500
was used for effecting the resolution of the volatile priority pollutants
(15). The chromatographic column was conditioned for 24 hrs at 220°C with
40 ml/min carrier flow (helium) prior to its use.
The GC/MS/COMP system was calibrated with regard to both mass and
intensity/quantity of priority pollutant in order to estimate the priority
pollutants on the sampling cartridges. These techniques are described in
Section 8.
RESULTS AND DISCUSSION
Distilled Water Studies
Table 8 presents the percent recovery of priority pollutants from de-
ionized-distilled water using three different vessel configurations. For
vessel configurations 1 and 2, the air bubble size was approximated at 1.0
cm while for vessel No. 3, the bubble size was ^0.3 cm. The percent re-
covery of the priority pollutants from vessel No. 2 was slightly better than
from vessel No. 1. In general, the highest recoveries were observed with
the vessel utilizing a glass frit for dispersing the air stream as it
entered into the liquid. A general trend was observed: those compounds
which had lower vapor pressures also subsequently gave lower recoveries.
Furthermore, those compounds which were water-soluble were difficult to
purge from the aqueous medium (j2.j£-, acrolein and acrylonitrile).
These data indicate that the recovery of priority pollutants from the
deionized-distilled water is influenced by the vessel configuration and
32
-------
TABLE 7. OPERATING PARAMETERS FOR GC-MS-COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber and valve
capillary trap - trap cycle
inject cycle
thermal desorption time
He purge rate
GC
MS
column
He carrier flow
GC/MS interface (glass jet
separator, transfer line)
scan range
scan cycle rate, automatic cyclic
emission current
electron energy
ion energy
lens voltage
extractor voltage
samples/amu
Available from Nutech Corp., Durham, NC.
Conditions for quadrupole instrument.
270°C
-195°C
+250°C
8 min
15 ml/min
60-160°C, 8°/min
40 ml/min
250°C
m/z 25+300
^2 sec
500 yA
70 eV
6 v
-100 v
8 v ...
1
33
-------
TABLE 8. PERCENT RECOVERY OF PRIORITY POLLUTANTS FROM
DEIONIZED/DISTILLED WATER FOR THREE VESSEL CONFIGURATIONS
Priority pollutant
1 , 1-dichloroethylene
1, 2-trans-dichloroethylene
1, 1-dichloroethane
chloroform
1,1, 1-trichloro ethane
carbon tetrachloride
1, 2-dichloroethane
trichloroethylene
broraodichloromethane
1, 2-dichloropropane
1,1, 2-trichloroethane
tetrachloroethylene
chlorobenzene
1,1,2, 2- tetrachloro ethane
broraoform
1, 3-dichlorobenzene
bis- (2-chloroethyl) ether
1, 2-dichlorobenzene
acrolein
acrylonitrile
benzene
toluene
Vessel-1
NDa
59 + 13°
86 + 19
77 + 22
ND
93+5
79+7
81+4
116 + 8
84+8
63 + 17
64 + 29
69 + 13
55+7
68 + 11
36 + 5
77 + 20
33 + 2
40 + 5
37 + 4
115 + 27
55
Vessel-2
82b
96+7
94 + 5
88 + 14
91
83 + 11
84 + 4
104 + 6
ND
66 + 20
63 + 4
65 + 17
106 + 3
58 + 2
85+7
59 + 29
72 + 18
47 + 13
41 + 3
37 + 9
ND
51
Vessel-3
67
103 + 2
98 + 1
87 + 7
ND
80 + 9
83+7
109 + 20
90 + 1
94 + 16
72 + 12
86+7
102 + 4
60 + 3
87 + 8
67 + 24
64 + 3
69 + 2
36 + 3
42 + 11
103 + 8
60
ND
not determined.
Single value.
r»
"Average of triplicate determinations.
34
-------
possibly by air bubble size. Since aeration of wastewater treatment basins
is conducted under many different conditions, it is difficult to relate the
percent air stripping of priority pollutants from an aqueous medium to a
particular set of conditions.
Methods-of-Addition Studies
Table 9 presents the results of the method-of—addition study for
priority pollutants in raw wastewater at the Durham, NC, Northside Treatment
Plant. The quantity of the priority pollutant added was in the ppb range.
The results are expressed in arbitrary units of detector response (peak
height or area). Where indicated, the data represent triplicate analyses.
Figures 9-12 present linear regressions for the methods-of-addition study on
this raw wastewater. As indicated in these figures, many of the compounds
gave linear regressions with x-y intercepts below zero. This indicates
possible sorption of the priority pollutants to organic solids. For some
pollutants a positive intercept was observed, and later GC/MS/COMP results
confirmed their presence in the original raw wastewater. These data clearly
indicate that, for the priority pollutants examined and even though a linear
response was observed, the priority pollutants are not recovered in a pre-
dictable fashion. These observations suggest that it is difficult to extra-
polate from air stream concentrations to the concentrations in the raw
wastewater using percent recoveries.
The methods-of-addition study indicated substantial quantities of
chlorobenzene, trichloroethylene, bromodichloromethane and 1,3-dichloro-
benzene to be present in the original raw wastewater.
Table 10 presents data for priority pollutants in activated sludge at
the Durham, NC, treatment plant. Where indicated, the analyses were per-
formed in triplicate. Figures 13-17 present the linear regression analyses
for the method-of-addition study on activated sludge. Trends similar to
those observed in the raw wastewater occurred. Even though a linear res-
ponse was observed, the x-y intercept was not zero, but was instead nega-
tive, indicating the loss of compounds which were added to the sludge (pro-
bably by sorption to the sludge or by degradation to other compounds). A
positive x-y intercept occurred too, suggesting that the priority pollutant
was in the original municipal wastewater. Because the methods of addition
experiments were conducted at different times, it was not possible to
compare the concentrations for the raw wastewater and activated sludge.
Percent Recovery of Priority Pollutants from Raw Wastewaters and Activated
Sludge
A series of experiments was conducted in order to ascertain the percent
recovery of priority (purgeable) pollutants at the ppb level from raw
wastewater and activated sludge from different wastewater treatment plants.
Table 11 presents the results for raw wastewater. In general the recoveries
decreased as the levels of the added priority pollutants decreased. The
highest recoveries were observed for bromodichloromethane (80%), trichloro-
ethylene (82%) and bromoform (71%), when added at 40 ppb. As might be
expected, the interpretation of these data is complicated by the fact that
35
-------
TABLE 9. METHODS-OF-ADDITION STUDY FOR PRIORITY POLLUTANTS
FROM RAW WASTEWATER
Priority pollutant
dichloromethane
1, 2-trans-dichloroethylene
1, 1-dichloroethane
chloroform
1, 1, 1-trichloroethane
carbon tetrachloride
1, 2-dichloroethane
trichloroethylene
bromodichloromethane
1 , 2-dichloropropane
1, 1, 2-trichloroethane
tetrachloroethylene
chlorobenzene
bromoform
1, 3-dichlorobenzene
1, 2-dichlorobenzene
acrolein
acrylonitrile
benzene
toluene
ethylbenzene
160
417a
1,187
1,374
477 + 69
147 + 3
854 + 129
323 + 7
1,062 + 184
516
799 + 312
251 + 49
1,961 + 101
3,225
3,715
2,594 + 80
23,840
I
1,252 + 664
7,068
5,310
4,640 + 46
Quantity
120
379
944 + 128b
1,800
-
122 + 50
691
276
907 + 313
455
590
204
1,545
2,997 2,
2,478
2,063 + 218
16,717
Id
679 + 291
5,254
4,594 2,
3,811
added (ppb)
80
_
305 + 25
707 + 3
191 + 14
102 + 1
-
65+1.4
507 + 101
253 + 3
-
Ill + 6
567 + 11
689 + 110
-
1,717
-
I
374 + 65
2,750 1,
545 + 18 1,
1,
40
117 + 33
140 + 18
304 + 110
134 + 12
-
138 + 2
57 + 1.3
309 + 66
153 + 34
174 + 21
76 + 6
389 + 3
-
723 + 131
-
-
I
186 + 13
447 +440
228 + 225
349 + 252
Single value, arbitrary units.
Average of triplicate determinations.
"»
"Not determined.
Interferents.
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TABLE 11. PERCENT RECOVERY OF PRIORITY POLLUTANTS FROM RAW
WASTEWATER FROM GRIT CHAMBER AT DURHAM WASTE TREATMENT PLANT
Percent recovery
Priority pollutant
1, 2-trans-dichloroethylene
1, 1-dichloro ethane
chloroform
1, 1, 1-trichloroethane
carbon tetrachloride
1, 2-dichloroethane
trichloroethylene
bromodichloromethane
1, 2-dichloropropane
1,1, 2-trichloroethane
tetrachloroethylene
chlorobenzene
bromoform
1, 3-dichlorobenzene
1, 2-dichlorobenzene
acrolein
acrylonitrile
benzene
toluene
ethylbenzene
160 ppb
92a
42
18+3
15 + 1
26 + 4
9 + 1
71 + 12
69
16 + 6
30+6
71 + 4
30
87
28 + 1
30
Id
45 + 23
34
25
8 + 1
120 ppb
98 + 13b
60
c
17 + 7
34
10
78 + 30
82
16
34
76
38
82
28 + 3
31
I
23 + 14
34
29
9
80 ppb
47 + 4
43 + 1
14 + 1
21+1
'
4 + 1
64 + 13
68 + 1
-
42 + 3
40 + 1
51+2
-
37
36
I
27 + 5
26
24 + 1
—
40 ppb
44+6
37 + 10
30 + 3
,. -
21 + 1
6 + 1
82 + 17
80 + 18
15 + 2
38 + 2
56 + 1
-
71 + 13
-
25 + 4
I
27 + 2
28 + 8
23 + 23
10 + 2
Single value.
Average of triplicate determinations.
°Not determined.
Interferents.
47
-------
the raw wastewater in some cases already contained the priority pollutant of
interest. The lowest recovery was observed for ethyl benzene at approxi-
mately 10%.
Table 12 gives the percent recovery from activated sludge. As might be
expected, in general these recoveries are considerably lower than those for
the raw wastewater. The data in Tables 11 and 12 correspond to the methods
of addition study which was presented earlier.
Tables 13-15 give additional recovery studies which were conducted on
raw wastewater and activated sludge from the South Burlington, NC, waste-
water treatment plant and from the Chapel Hill, NC, plant. In contrast,
these experiments were conducted at the 1 ppb level. A high degree of
variability can be expected in the percent recovery of priority pollutants
from raw wastewater and activated sludge. For these reasons and for reasons
cited earlier, it is virtually impossible to accurately predict (±2%) the
concentrations of priority pollutants in the raw wastewater or activated
sludge based on their level in the air stream.
48
-------
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-------
TABLE 13. RECOVERY OF PRIORITY POLLUTANTS FROM RAW WASTEWATER FROM
GRIT CHAMBER AT SOUTH BURLINGTON, NC WASTEWATER TREATMENT PLANT
Priority pollutant
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
1, 2-dichloroethane
carbon tetrachloride
bromodichloromethane
benzene
bromoform
chlorobenzene
1 , 2-dichlorobenzene
ng/ cartridge
91 + 21b
131 + 27
NDC
44 + 19
251 + 71
106 + 45
160 + 34
214 + 23
208 + 47
120 + 13
156
Q
ppb (observed)
0.23 + 0.05
0.33 + 0.07
ND
0.11 + 0.05
0.63 + 0.18
0.27 + 0.11
0.40 + 0.08
0.53 + 0.05
0.52 + 0.12
0.30 + 0.03
0.04
% recovery
23 + 5
33+7
0
11 + 5
63 + 18
27 + 11
40 + 8
53 + 5
52 + 12
30 + 3
40
Spiked at 1 ppb.
Average of triplicate determinations.
"ND
not detected.
50
-------
TABLE 14. RECOVERY OF PRIORITY POLLUTANTS FROM ACTIVATED SLUDGE FROM
SOUTH BURLINGTON, NC WASTEWATER TREATMENT PLANT
Priority pollutant
dichlorome thane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1,1-trichloroethane
carbon tetrachloride
bromodichloromethane
benzene
trichloroethylene
bromoform
tetrachloroethylene
toluene
e thy Ib en z ene
chlorobenzene
1, 2-dichlorobenzene
ng/ cartridge
174 + 3b
15+0.8
NDC
ND
ND
175 + 44
214 + 13
47 + 12
67 + 0.5
134 + 13
244 + 13
79 + 9
527 + 145
314 + 28
295 + 33
78+8
179 + 2
f\
ppb (observed)
0.44 + 0
0.04+0
ND
ND
ND
0.44 + 0.11
0.54 + 0.03
0.12 + 0.03
0.17 + 0
0.33 + 0.03
0.61 + 0.08
0.20 + 0.03
1.31 + 0.36
0.78 + 0.07
0.74 + 0.08
0.19 + 0.02
0.45 + 0
% recovery
44 + 0
4 + 0
0
0
0
44 + 11
54 + 3
12 + 3
17 + 0
33 + 3
61 + 8
20 + 3
131 + 36
78+7
74+8
19 + 2
45 + 0
aSpiked at 1 ppb.
Average of triplicate determinations.
CND = not detected.
51
-------
TABLE 15. RECOVERY OF PRIORITY POLLUTANTS FROM RAW WASTEWATER FROM
GRIT CHAMBER AT CHAPEL HILL, NC MUNICIPAL WASTE TREATMENT PLANT
Priority pollutant
1, 1-dichloroethylene
1, 2-trans-dichloroethylene
1, 2-dichloroethane
bromodichloromethane
1, 2-dichloropropane
bromoform
chlorobenzene
1, 2-dichlorobenzene
ng/ cartridge
236 + 38b
196 f 26
329 + 49
271 + 5
170 + 5
256 + 5
235°
278 + 48
ppb (observed)
0.59 + 0.09
0.49 + 0.06
0.82 + 0.12
0.68 + 0.02
0.43 + 0.08
0.64 + 0.02
" 0.59
0.69 + 0.12
% recovery
59 + 9
49 + 6
82 + 12
68 + 2
43 + 8
64 + 2
59
69 + 12
Spiked at 1 ppb.
Average of triplicate determinations.
^
"Single value.
52
-------
SECTION 7
DESIGN AND FABRICATION OF SAMPLING SYSTEM FOR PRIORITY POLLUTANTS
EMITTED FROM MUNICIPAL TREATMENT FACILITIES
INTRODUCTION AND DESIGN CRITERIA
The sampling unit (Fig. 18) was designed for accurate sampling of
purgeable organic priority pollutants in municipal sewage treatment facili-
ties. Primary use of this unit is for sampling gaseous evolution from
aeration tanks, although with minor modification it can also be used in
other areas such as the grit chamber.
The aeration tank may be considered a surface source of non-homogeneous
character where the rate of gas evolution as well as the concentration of
organics varies from point to point. Time dependence and other variability
may also be expected. Obtaining meaningful data under these conditions
requires that the total volume of gas evolving from the surface be deter-
mined. The sampling head (Fig. 19) must therefore define a certain surface
area and channel all gases emitted through the appropriate flow monitors.
A skirt extending into the liquid defines the source area and provides the
low pressure buildup necessary to force the gas through the sampler.
Initially a pressure head allowance of 2 in. of H_0 was provided. This was ade-
quate to handle a flow rate through the sampler or up to 30 &/min. How-
ever, after field testing the unit, an additional 4 in. was added to the
skirt because of surface turbulence that was encountered. The lower limit
on the flow rate was 'determined by the amount necessary to assure that
enough gas would be flowing through the system to use three cartridges
simultaneously. Based on considerations described elsewhere, this lower
flow limit with a design safety factor would be about 1 &/min. F°r air-
volume to liquid-volume ratios for typical aeration tanks, a surface area
of 1 ft2 should evolve a gas flow within the range of 1 to 30 5,/min. The
sampling head was made long and narrow instead of square to provide a
degree of integration for the variation of emission from center to side of
a typical tank.
It was anticipated that turbulence and foaming on the surface would
cause non-gaseous' material to be carried into the sampling system. Con-
sequently a baffle system was designed to change the direction of flow,
raise the air velocity, and provide liquid impingement and runoff. This
system was adequate for the situations that were encountered in the field
testing program.
The gaseous sample encountered in this situation is saturated with
water vapor. To prevent condensation, the sample line is heated to 40°C.
53
-------
DIGITAL DISPLAY-
TEMP/MASS FLOW
READOUT SWITCH
POWER AND PUMP
SWITCHES
CONTROL CONSOLE
SOLENOID VALVE
SWITCHES
.METERING VALVES
DRY GAS METER
Figure 18. Schematic of sampler system for grit chambers and aeration tanks.
54
-------
o
M
a
•H
J-i
O
CO
60
•H
55
-------
This temperature prevents condensation and at the same time is not hot
enough to cause decomposition and loss of pollutants. Likewise the sample
manifold is held at the same temperature. Although breakthrough volumes
are lower than at ambient temperature, it would not be desirable to con-
dense moisture in the cartridges. The remainder of the system relies on
the residual heat of the gas- to maintain it above the dew point.
Pre-cartridge sample contact areas are stainless steel or
maintain sample integrity. The sample transfer line from the sample head
to the console is heated to prevent condensation at low ambient temperatures.
In the console samples are collected on three Tenax cartridges—also pro-
tected in a temperature-controlled -chamber to prevent condensation and to
maintain cartridge efficiency during ambient temperature changes during the
sampling period.
Sample line temperature and mass flow through the cartridges can be
read on a digital display for accurate data logging. Excess gas flow from
the sample head that is not diverted through the cartridges is registered
on a dry gas meter. Three metering valves adjust the flow through the
cartridges. One or more of the flow rates through the cartridges can be
monitored without changing flow settings on the mass flow meter by switch-
ing activated solenoid valves to individual cartridges.
The stainless steel fabrication of the sample head is also necessary
to resist corrosion. It was designed to sample precisely a 1 ft2 area
(Fig. 19). Gas bubbles rising near but not within the defined sample area
are deflected by a submerged skirt and flanges. Water is prevented from
entering the sample collection line by baffles inside the head.and four
polyethylene—foam flotation pads provide proper submersion of the skirt and
stability in heavy bubble activity.
OPERATION
Operation of the system for sampling aeration tanks can be described
in three phases: equipment placement'and preparation, set-up for proper
flow, cartridge installation and sampling.
Equipment Placement and Preparation
The initial step in this procedure was selecting an appropriate loca-
tion for the sample head and console. Since tank design and operation vary
considerably, care must be exercised to place the units where sufficient
bubble activity is present and where the console and sample head can be
located within a few feet of each other (the sample line between the head
and console is short to maintain accuracy) and within reach of AC power.
The sample head can be secured in location by attaching the support arm to
a railing. Additional stability can be obtained by attaching ropes to eye
bolts located at the ends of the sample head.
Bubble flow rates vary considerably from site to site; however, under
typical aeration rates, flow is in the range of 2.5 &/min/ft surface area.
The rate can be determined by passing total flow through the dry gas meter
56
-------
for a short period of time, about 10 minutes. During this period the
umbilical line and cartridge chamber should stabilize to temperature.
Flow Calibration
Flow through individual cartridge holders was set by adjustment of the
metering valves (Pig. 20). With the pump switch on, the solenoid valve
corresponding to the holder of interest on, and the digital panel meter
switch in the "Mass Flow" position, the metering .valve was slowly opened
until the mass flow indication reached the desired level. This procedure
was repeated for each of the cartridge holders to establish flow through
each holder.
When flow rates have been set to the desired level, the solenoid
valves could be shut off without disturbing flow settings, and prepared
cartridges can be installed for sampling.
Temperature/Mass Flow Readout
The front panel digital display (Fig. 18) can be switched to read
either mass flow or umbilical (transfer line) temperature. In the mass
flow position the display reads directly in ml/minute; however, in the
temperature position the display reads deviation from set point in degrees
centigrade.
Temperature Controls
The umbilical temperature was maintained (factory set) at 40°C by a
proportional solid state electronic temperature controller (Fig. 21). The
set point was adjustable by screw driver on the printed circuit card but it
should not require resetting under normal operating conditions. Cartridge
chamber temperature is maintained by a self-contained controller/heater and
is not adjustable.
SPECIFICATIONS AND COMPONENTS
Power: 115 VAC, 50/60Hz, 5A
Weight: Control Console - 55 Ibs (25 kg)
Sample Head - 28 Ibs (12.7 kg)
Dimensions: Control Console - 62 cm H x 40 cm W x 27 cm D
Sample Head - 20 cm H x 117 cm W x 81 cm D
Vacuum Pump: 0.5 scfm @ 23 in. Hg
3
Mass Flow Measurement: 0 - 500 cm /min
3
Dry Gas Meter: 100 cubic meter total, readable to 0.0001 m .
Table 16 lists the components for the sampler, and Figures 18-21 depict
schematics of the sampling system.
57
-------
HEADED UMBILICAL
CARTRIDGE MANIFOLD
EXHAUST
VALVE (orWf I I IN
MASS FLOW
METER
Figure 20. Diagram of pneumatics in sampler system.
58
-------
IIOV FUSE
PUMP SWITCH
PUMP
HEATER
rLTLTL..
24V MASS
DC FLOW
DETECTOR
SOLENOID VALVES
Figure 21. Schematic of electronics in sampler system.
59
-------
TABLE 16. PARTS LIST FOR AERATION TANK SAMPLER
Nutech part #a
851-001
851-002
851-003
851-004
851-005
851-006
851-007
851-008
851-009
851-010
851-011
851-012
851-013
851-014
851-015
851-016
851-017
851-018
851-019
851-020
851-021
851-022
851-023
851-024
851-025
851-026
851-027
851-028
851-029
851-030
Description
cabinet enclosure #201-002
sample chamber #320-001
stainless sample hood
polyethylene foam' pad
heated TFE sample line
quick connect, 1/2" female
quick connect, 1/2" male
thermocouple, type K
dry gas meter w/ thermometer installed
mass flow meter
24 VDC power supply
diaphragm pump
temperature control board
relay w/socket, 110 VAC, DP
4-terminal barrier strip
switch, SPST
fuse holder
LCD display
power cord
male AC connector
female AC connector
switch, DPDT
valve, flow control
valve, solenoid, 110 VAC
stainless manifold, 4 port
stainless manifold, 5 port
check valve
cartridge assembly w/TFE union
sample manifold, 3 port TFE
1/4 NPT nipple, TFE
Quantity
1
1
1
4
1
1
1
1
#221-028 1
1
1
1
1
1
2
2
2
1
1
1
1
1
3
3
1
1
1
3
1
3
(continued)
60
-------
TABLE 16 (cont'd.)
Nutech part #a
851-031
851-032
851-033
851-034
851-035
851-036
851-037
851-038
851-039
851-040
851-041
851-042
851-043
851-044
851-045
851-046
851-047
851-048
851-049
851-050
851-051
851-052
851-053
851-054
851-055
Description
bulkhead union, 1/4"
stainless L
TFE reducer, 1/2" x 7/16"
hose clamp, 7/16"
switch, SPST
indicator lamp
1" foam insulation
piano hinge, 8"
deleted
screws, misc.
house coupling, 1/2 NPT
pot, IK, 20T
resistor 1%, 8.2K
thermocouple connector, male, type K
thermocouple connector, female, type K
thermocouple connector, mounting bracket
fuse, 2A
fuse, 3A
crimp terminal
vinyl tubing, 3/16 x 5/16"
vinyl tubing, 7/16 x 5/8"
cabinet base #201-001
control panel #201-004
cabinet handles #201-008
knockout jar
Quantity
3
3
1
1
3
1
2 ft2
1
17
1
1
1
1
1
1
1
30
15 ft
3 ft
1
1
3
1
or its equivalent.
61
-------
SECTION 8
INSTRUMENTAL (GC/MS/COMP) METHODS OF ANALYSIS
INTRODUCTION
As part of the overall methodology development for collection and
analysis of "purgeahle" priority pollutants emitted from municipal treat-
ment facilities, it was necessary to delineate the instrumental methods to
be used. Under Section 9.0 the previously reported (15) methods for analy-
sis of priority pollutants in industrial effluents using gas chromatograpy/
mass spectrometer/computer (GC/MS/GOMP) were applied. The purpose of this
study was to further define these methods and operating parameters.
The results presented in Section 9.0 indicated that the previously
reported techniques were compatible with the analysis of purgeable priority
pollutants occurring in the air streams from municipal treatment facili-
ties. This section addresses the method of quantification and detection
limits for priority pollutants on Tenax GC sampling cartridges.
EXPERIMENTAL
Instrumental Parameters (GC/MS/COMP)
A Finnigan 3300 GC/MS with a PDP-12 computer was used for defining the
instrumental operating parameters.
Instrumental Conditions—
For the analysis of priority pollutants collected on Tenax GC the
operating parameters given in Table 17 were used. The thermal desorption
chamber and the six-port Valco valve were maintained at 270°C. The glass
jet separator was at 250°C. The mass spectrometer was set to scan from 25-
300 amu. The helium purge gas through the desorption chamber was 15 ml/min.
The nickel capillary trap on the inlet manifold was cooled with liquid Na«
In a typical thermal desorption cycle, a sampling cartridge was placed in a
preheated desorption chamber and the helium gas was passed through the
cartridge to purge the vapors into the liquid- N2- coo led trap. Aftej: desorp-
tion was completed (8 min), the six-port valve was rotated, and the tempera-
ture on the capillary loop was raised rapidly (>150°/min). Carrier gas
then transferred the vapors onto the gas chromatographic column. The
chromatographic column was held for 3 min at 60°C, programmed 8°/min to
160°C and, held until all compounds were eluted. The chromatographic column
used here was previously described (see Section 5).
62
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TABLE 17. OPERATING PARAMETERS FOR GC-MS-COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber and valve
capillary trap - trap cycle
inject cycle
thermal desorption time
He purge rate
GC
MS
column
He carrier flow
GC/MS interface (glass jet
separator^ transfer, line)
scan range
scan cycle rate, automatic-cyclic
emission current
electron energy
ion energy
lens voltage
extractor voltage
samples/amu
270°C
-195°C
+250°C
8 min
15 ml/min
60-160°C, 8°/min
40 ml/min
250°C
m/z_ 25->300
^2 sec
500 pA
70 eV
6 v
-100 v
8 v
1
Conditions for quadrupole instrument.
63
-------
Operation of the GC/MS/COMP System—
Typically the mass spectrometer was first set to operate in the repe-
titive scanning mode. In this mode, the quadrupole automatically scanned
upward from a preset low mass to a high mass value. The scan was completed
in M. sec. At this time the instrument automatically reset itself to the
low mass position in preparation for the next scan, and the information was
accumulated by an on-line dedicated computer (PDP-12) and written onto a
disk. The scan-plus-reset period was ^2 sec/scan cycle and was repetitivelv
executed throughout the chromatographic run. Thus data were accumulated as
a continuous series of mass spectra throughout the chromatographic run.
The system was calibrated daily by introducing the standard substance
heptacosafluorotributylamine and determining the time of appearance of
known standard peaks in relation to the scanning field. The calibration
curve thus generated was stored in the computer memory. This calibration
served only to assign masses over the scanning range.
With the instrument continuously scanning, the sample was then injected
and automatic data acquisition was initiated. Upon completion of the
chromatographic run, ^800-1400 spectra accumulated on the disk could be
transferred to magnetic tape which was subsequently processed. Depending
on the information required that day, data were either processed immediately
or additional samples were run, the data were stored on magnetic tape, and
the results were examined at a later time.
The mass spectral data were processed in the following manner. First
the original spectra were scanned, and integrated ion current information
was extracted. The reconstructed ion current profile was then'plotted
against time on an electrostatic recorder. The information generally
indicated whether the run was suitable for further processing since it
provided some idea of the number of unknowns in the sample and the reso-
lution obtained using the particular GC column conditions.
Detection Limits—
Using the characteristic ions given in Tables 18, the detection limits
for a number of pure authentic priority pollutants loaded onto Tenax GC
sampling cartridges were determined by executing the entire process of
thermal desorption, gas chromatography and mass spectrometric detection.
Standards of the priority pollutants were loaded onto the Tenax GC sampling
cartridges using a previously described permeation system (see Section 5).
This process involved the repetitive injection of decreasing amounts of
each of the priority pollutants and estimation of the limit of detection
based on ca a 4:1 signal-to-noise level. The limit of detection therefore
is not the quantifiable limit.
Relative Molar Response (RMR) Factors—
Quantification was achieved using standards which were loaded onto the
Tenax GC sampling cartriges prior to instrumental analysis by means of the
permeation line described earlier and using a unique mass-cracking ion in
the mass spectrum of the external standard. In order to eliminate the need
to obtain complete calibration curves for each priority pollutant for which
quantitative information was desired, the method of relative molar response
64
-------
(RMR) factors was used (8,13). Successful use of this method requires
information on the exact amount of standard added and the relationship of
RMR, , , to the RMR, , , x. The method of calculation is as follows:
(unknown) (standards)
(1) RMR
A , /Moles ,
_ unk unk
'unknown/standard A ,/Moles ,.
A = m/z^ peak area, determined by integration or triangulation.
The value of RMR is determined from at least three independent analyses.
A , /g , /GMW 1
- unk unk unk
A = WjZ peak area, as above
g = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
(3) g.
3unk
A , -GMW , 'g ^,
unk unk °std
A 'GMW 'RMR
std std unk/std
Upon acquiring full spectra throughout the chromatographic run, selec-
ted ions were presented as mass fragmentograms using computer software
programs which allow the representation of ion intensity vs. time (Table
18). The RMR and quantity of priority pollutant in the samples were
estimated using this technique.
RESULTS AND DISCUSSION
Table 19 presents the results of the limit of detection (LOD) study
for a series of priority pollutants. The range was approximately from 0.1
ng to 50 ng. These detection limits were determined for the ion given in
this table.
Table 20 presents the relative molar response factors which were
determined for several priority pollutants using the indicated selected m/z
ions. The data represent an average of triplicate determinations. In
general, the reproducibility is within 10%. The RMR factors were redeter-
mined approximately 3 weeks later, and these data were within +20% of the
values given in Table 20. Thus it was concluded that during the routine
analysis of many samples, cartridges containing calibrated amounts of
priority pollutants should be incorporated into the sample set at a fre-
quency which constitutes M.0% of the sample load. In this manner, relative
molar response factors can be generated over a period of time and used to
account for variations in the GC/MS/COMP instrumentation (e_..g_., changes in
high-low mass sensitivity with ion source contamination).
65
-------
TABLE 18. CHARACTERISTIC M/Z IONS SELECTED FOR
QUANTIFICATION OF PRIORITY POLLUTANTS
Priority pollutant
chloromethane
dichlorodif luoromethane
bromomethane
vinyl chloride
chloroethane
dichloromethane
tr ichloro f luoromethane
1, 1-dichloroethylene
1, 1-dichloroethane
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1,1, 1-trichloroethane
carbon tetrachloride
broraodichloromethane
bis- (chloromethyl) ether
1, 2-dichloropropane
trans- 1, 3-dichloropropene
trichloroethylene
dibromochloromethane
cis-1, 3-dichloropropene
1, 1, 2-trichloroethane
benzene
2-chloroethylvinyl ether
bromoform
1, 1, 2, 2-tetrachloroethylene
1,1,2, 2-tetrachloroethane
toluene
chlorobenzene
M.W.
50.5
120.9
95.0
62.5
64.5
84.9
137.4
97
99
97
119.4
99
133.4
153.8
163.9
115.0
113
113
113.4
208.3
113.4
78.1
106.6
252.8
165.8
167.9
92.1
112.6
1st Ion
m/z* (I)b
50(100)
101(13)
94(100)
62(100)
64(100)
84(86)
101(100)
86(80)
63(100)
96(90)
83(100)
98(23)
97(100)
117(100)
127(13)
79(100)
112(4)
75(100)
130(90)
127(78)
75(100)
97(100)
78(100)
106(18)
173(100)
165(78)
168(6)
91(100)
112(100)
2nd Ion
m/z* (I)b
52(33)
103(9)
86(94)
64(33)
66(33)
86(55)
103(66)
93(53)
65(33)
61(100)
85(66)
100(15)
99(66)
119(96)
129(17)
81(33)
114<3)
77(33)
132(85)
208(13)
77(33)
99(63)
79(6)
63(95)
175(50)
166(100)
137(7)
92(78)
114(33)
3rd Ion
/Si / T~\ ti
z (I)
-
87(33)
-
-
-
49(100)
-
61(100)
83(13)
98(57)
-
62(100)
-
121(30)
85(66)
-
65(33)
-
97(66)
206(10)
-
132(9)
-
-
252(11)
129(64)
133(7)
-
-
(continued)
66
-------
TABLE 18 (cont'd.)
Priority pollutant
ethylb enzene
acrolein
acrylonitrile
perf luorobenzene
perf luorotoluene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
M.W.
106.2
56.1
53
186
235
1st Ion
m/z (I)
106(33)
56(83)
53(99)
186 (100)
186(100)
146 (100)
146(100)
2nd Ion
m/z (I)
91(100)
55(65)
52(75)
-
263(100)
150(10)
150(11)
3rd Ion
m/z (I)
-
-
51(32)
-
117(13)
-
-
to charge ratio
Ion intensity, percent
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TABLE 20. RELATIVE MOLAR RESPONSE FACTORS FOR SEVERAL PRIORITY POLLUTANTS
USING SELECTED M/Z IONS
Priority pollutant
methyl bromide
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1,1-trichloroethane
carbon tetrachloride
bromodichlorpmethane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
toluene
ethylbenzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
m/z_
94
84
96
53
61
83
98
97
117
127
112
78
130
171
170
93
106
112
150
150
ig-PFB
(m/z-186)
0.104 + 0.008a
0.139 + 0.002
0.341 + 0.049
0.037 + 0.005
0.098 + 0.016
0.093 + 0.013
0.016 + 0.005
0.119 + 0.004
0.075 + 0.005
0.017 + 0.004
0.004 + 0
0.024 + 0.032
0.071 + 0.017
0.036 + 0.007
0.019 + 0.003
0.019 + 0.002
0.254 + 0.047
0.341 + 0.048
0.039 + 0.002
0.015 + 0.001
1S-PFT
(m/z^-236)
0.076 + 0.002
0.104 + 0.007
0.249 + 0.041
0.027 + 0.003
0.070 + 0.007
0.071 + 0.016
0.011 + 0.001
0.095 + 0.013
0.054 + 0.004
0.013 + 0.003
0.032 + 0.004
0.187 + 0.038
0.052 + 0.013
0.026 + 0.004
0.013 + 0.002
0.014 + 0.002
0.184 + 0.036
0.248 + 0.039
0.0295 + 0
0.0115 + 0
aAverage of triplicate determinations.
70
-------
SECTION 9
APPLICATION OF DEVELOPED METHODS TO THE COLLECTION AND ANALYSIS OF
"PDRGEABLE" PRIORITY POLLUTANTS EMITTED FROM
MUNICIPAL TREATMENT FACILITIES
INTRODUCTION
The major objective of this program has been to develop, validate and
apply a method to the collection and analysis of priority pollutants emit-
ted from municipal treatment facilities. The procedure was to represen-
tatively sample air streams passing through wastewater in grit chambers and
aeration basins and to analyze those representative samples for volatile
toxic organics. The previous sections addressed the development and evalua-
tion of individual facets of the collection and analysis systems. This
section presents a further evaluation of the procedure and its application
to different types of aeration systems including pure oxygen (closed chamber)
activated sludge, conventional activated sludge, conventional grit chamber,
and aerated grit chambers. One major aim was to determine the amounts of
priority and other pollutants stripped from the water by an air flow in
grit chambers and aeration basins in order to define the sampling volume
vs. sample quantity for GC/MS/COMP analysis.
This section discusses the cumulative effort of the individual facets
of the program previously described in Sections 5-8 and the application of
the developed method to the collection and analysis of priority pollutants
in air streams.
EXPERIMENTAL
Sampling of Open Aeration Basins
Integrated sampling of the air stream passing through wastewater at
municipal treatment plants was accomplished using the prototype Nutech
sampler (Nutech Corp., Durham, NC) 'described under Section 7. Flow rates
were maintained at prescribed rates using the variable critical orifices.
The flow through each of the three sampling cartridges and the total flow
through all cartridges were monitored with a calibrated mass flow meter.
The total flow from the aeration basin (minus the sampled volume) was
registered on a dry gas meter; only a fraction (up to 30%) of.the air stream
to the sampling unit was sampled by the three Tenax GC cartridges.
Typically, sampling of aeration basins involved placing on the wa,ste<-
water surface the gas sampling shroud which was supported by flotation
71
-------
collars and held in position by support arms fastened to the guard rails.
The aeration rate passing through the wastewater was measured as a total
gas flow into the gas meter plus the total volume sampled. The gas flow
was expressed as £/min/ft2. Because the aeration rate can be highly vari-
able across a basin, it was necessary to determine the aeration rate prior
to sampling by simply passing the total flow of the drying gas meter for a
short period of time (^10 min).
Sampling volumes of 1, 3 and 5 A/cartridge were used in these studies
to determine the quantity of organic vapors that should be collected with-
out overloading or saturating the instrumental analysis system. Triplicate
cartridges were used in sampling.
Sampling was performed at the grit chamber and aeration basins at the
South Burlington, NC and Durham, NC wastewater treatment plants. The
sampling protocols are given in Table 21.
Sampling of Closed (Pure Oxygen) System
Continuous sampling for the priority pollutants in the vent from a
closed chamber was accomplished using a Nutech Model 221-1A portable sampler
(Nutech Corp., Durham, NC). The total flow was monitored through a cali-
brated flow meter to integrate the flow sample from all cartridges. The
portable sampling unit was operated on a 12 v storage battery and was
capable of continuous operation for a period of up to 24 hrs. Duplicate
cartridges were deployed at the exhaust vent. The sampling head was connec-
ted to a vacuum- line of ^20 ft so that the sampler could be positioned at a
distant location from the pure oxygen vent.
A 1-& gas sample was taken over a period of 5 min.
Qualitative Analysis by Capillary GC/MS/COMP
Qualitative analysis was performed with a CH-7 GC/MS system equipped
with a 620L computer. The organic vapors which were collected on the Tenax
GC sampling cartridge were subjected to thermal desorption followed by
capillary gas chromatography for the resolution of .the complex mixture. An
SE-30 stationary phase coated on a glass SCOT capillary (12,13) which was
programmed from 25°C-240°C at 4°/min was used for effecting this resolu-
tion. The carrier flow (helium) was 2.5 ml/min. The operating parameters
presented in Table 7 were used for the analysis of this sample.
Prior to running unknown samples, the system was calibrated by intro-
ducing a standard substance, perfluorokerosene, into the instrument and
determining the time of appearance of the known standard peak in relation
to the scanning field. Calibration curves which are thus generated were
stored in computer memory. This calibration served only to calibrate the
mass ion over the mass scanning range. The next stage of the-data proces-
sing involved the mass conversion of the spectral peak times to peak masses
which was done directly via the dual disk system. A mass conversion was
accomplished by use of the calibration table obtained previously using
perfluorokerosene (normally one set of the calibration data was sufficient
72
-------
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for an entire day's data processing since the characteristics of the Hall
probe were such that calibration variation was <0.2 amu/day).
The identity of the components in the sample was assigned on a grated
scale. Positive identification was assigned for those compounds for which
the observed spectrum matched library spectra and/or indices of tabulated
spectra and the elution time and temperature corresponded with that of an
authentic compound. For many cases where the isomeric forms could not be
distinguished, the name of the compound as an isomer was indicated. In
many cases only an empirical formula could be assigned since the mass crack-
ing pattern of isomers were very similar (retention indices could not be
available). In some cases a tentative identification was assigned when the
mass cracking pattern yielded a similar match and no retention index was
available for that compound.
Quantitative Analysis by GC/MS/COMP
The calibration of the GC/MS system for quantitative analysis of
priority pollutants involved spiking Tenax GC sampling cartridges with
known amounts of priority pollutants and internal standards perfluorobenzene
and perfluorotoluene utilizing the previously described permeation system
(10). Procedure for calibrating the GC/MS system and the determination of
BMR's was also previously described (Section 8).
A Finnigan Model 3300 GC/MS system equipped with a PDP/12 computer was
used. This system was described in Section 8.
RESULTS AND DISCUSSION
Figure 22 presents the GC/MS/COMP chromatographic profile of the
volatile organics which were identified in air streams from an aeration
basin at Durham, NC treatment plant. Approximately 100 discernable compo-
nents were detected. Table 22 presents the volatile organics which were
identified in the air stream. Several sulfur compounds and chlorinated
hydrocarbons were identified. However, the majority of the components were
hydrocarbons and alkyl-aromatics. Even using a 100-m glass SCOT column
coated with SE-30, the resolution was inadequate to completely separate all
the components, particularly those occurring between elution temperatures of
135°-195°C. Despite the complexity of the sample, many of the organics
were identified. Furthermore, the use of the chromatographic conditions
employing the packed column described earlier is effective in separating
the volatile (purgeable) priority pollutants when used in combination with
mass chromatography. The presence of many of the priority pollutants of
interest which were identified in this sample confirms the previous methods-
of-addition experiments since the previous data indicated the presence of
priority pollutants which complicated the recovery studies.
Table 23 presents the analysis for priority pollutants in air streams
from the grit chamber at South Burlington, NC. The sampling system descri-
bed in Section 7 was used to sample the grit chamber (the sampling protocol
was given in Table 21). The data indicate substantial concentrations
74
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TABLE 22. VOLATILE ORGANICS IDENTIFIED IN AIRSTREAM FROM AERATION
BASIN (PLUG FLOW) AT DURHAM, NC PLANT3
Chroma Co-
graphic
peak no.
1
2
2A
3
4
5
6
6A
6B
7
7A
7B
7C
8
8A
9
9A
10
10A
10B
11
12
12A
13
14
14A
14B
15
ISA
16
17
17A
18
ISA
19
20
21
22
22A
23
23A
24
25
26
Elution
tccip*
(*C)
58
62
64
69
71
72
73
74
78
79
79
80
81
83
84
85
85
88
87
89
91
94
94
95
96
97
98
98
100
101
103
103
107
108
109
111
115
119
119
120
122
123
124
130
Compound
°°2
acetaldehyde'-f C,Hg isomer
•ethyl ethyl 'ether (tent.)
acetone
diethyl ether
dimethyl sulphide
dichloromethane
carbon disulphide
C,H,0 aldehyde isomer
1, 1-dichloroethane
vinyl acetate (tent.)
•ethyl vinyl ketone
•ethyl ethyl ketone
hexafluorobenzene (eS) +
dichloroethylene isomer
ii-hexane
chloroform
ethyl acetate
perfluorotoluene (e$)
aethylcyclopentane
1, 2.-dichloroethane
ltl, 1-trichloroethane
benzene
carbon tetrachloride (traces)
(tent.)
1-butanol
CyHj, isomer
C.H...O aldehyde isomer
3-Bethylhexane
n_-pentanal
C-Hj-O isomer (tent.)
trichloroethylene
ii-heptane
2-thiapentane
ethyl isopropyl ether (tent.)
C7H14 isoner
dimethyl disulphide
acetic acid
toluene
ii-hexanal
CgH, , isomer
CgH.g isomer
CgH20 isomer
Ei-octane
cetrachloroethylene
trimethylcyclohexane
hromato-
;raphic
eak no.
27
28
29
30
30A
31
32
33
34
35
36
37
37A
38
39
40
40A
40B
40C
41
41A
42
42A
42B
43
43A
43B
44
45
45A
46
46A
47
47A
48
49
49A
49B
50
50A
SOB
50C
Elution
temp .
CO
131
134
134
135
136
137
139
140
140
141
142
143
143
145
146
147
148
148
149
149
151
151
152
153
153
154
154
155
155
156
156
157
158
158
159
160
161
161
162
162
163
164
Compound
CgH^ a isomer
ethylbenzene
trimethylcyclohexane isomer
xylene isomer
CgH2Q isomer
CgH2g isomer
CgH 8 isomer
o-xylene
CgH.g isomer
methylethylcyclohexane isomer
methylethylcyclohexane isomer
rr-nonane + alkyl butyrate
(tent.)
^10H20 *sonier
CgHjo isomer
C10H22 iBomer
CqH., + CqH,fi Isomers
C10H22 lsomer
C10H20 lsomer
CgH^g isomer
<'10H22 :tso'Iier
benzaldehyde (traces)
C10H20 lsomer + 'n-propyl-
benzene (traces)
C10H18 is°mer
ethyltoluene isomer
C.QH22 isomer
C10H20 ^somer
1,3,5-trimethylbenzene
C10H22 isolner
C10H20 is°aer
C10H22 *Bomer
^-ethyltoluene
C10H18 isomer
C10H20 isomer
C10H20 ^soner
1,2,4-trifflethylbenzene +
C10H20 :1-sol!ier
C10H20 isomer
dichlorobenzene isomer
nj-decane
dichlorobenzene +
isomer
C,-alkyl benzene isomer
C11H22 lsoner
C,-alkyl benzene isomer
(continued)
76
-------
TABLE 22 (cont'd.)
Chromato-
graphic
peak no.
51
51A
52
52A
53
54
55
55A
56
56A
57
57A
58
59
59A
59B
60
61
62
63
64
64A
64B
65
65A
66
67
67A
68
68A
68B
68C
69
69A
70
70A
Elution
temp.
165
165
165
166
166
167
167
167
168
168
169
169
170
170
171
171
172
172
173
173
174
174
175
175
176
176
177
178
178
179
180
181
181
182
183
183
Compound
1,2, 3-trinethylbenzene
C^-alkyl benzene isomer
C11H24 isOTier
C11H24 lsomer
dichlorobenzene isomer
C. iHj, isomer
C. nil. f isomer
C10H18 isomer
C,~alkyl cyclohexane isomer
C. -,#22 isoiner
C11H24 isomer
C.-alkyl benzene isomer
C,-alkyl benzene + C, -l^
isomers
C.-alkyl benzene isomer
C11H22 isomer
C11H24 isomer
£^22 isoner
C.-alkyl benzene +
C. -H,, . isomers
C10H18 isolner
ii-nonanal
C11H24 isolner
C.-alkyl benzene isomer
C....H22 isoiner
C^-alkyl benzene +
C,H_-benzene isomers
C12H22 isomer
C11H22 lsomer
C11H22 lsomer
C12H24 isomer
la-undecane
C.-alkyl benzene isomer
C12H26 isomer
C.-alkyl benzene isomer
C12H26 isomer
^11^20 ^somer
C.Ji~. isomer
Cj-alkyl benzene isomer
Chromato-
graphic
peak no.
71
71A
72
73
73A
74A
75
76
76A
76B
77
78
78A
78B
79
80
81
82
83
84
85
86
86A
87
88
90
91
92
93
93A
94
95
96
97
Elution
temp.
184
184
185
186
186
187
188
190
190
191
192
193
195
195
196
198
200
200
202
203
205
207
207
208
211
216
217
218
219
221
222
229
231
235
Compound
C12H26 + alfcy1 Pneno1 (tent.)
isomers -
Cj-alkyl benzene isomer
C11H20 + C12H24 isomer
C^H^-benzene + (-'i2^24 isomers
C^-alkyl benzene isomer
C^-alkyl benzene isomer
C, ^nf isomer
j./ jib
C10H18 isomer
trichlorobenzene isomer
C- 2^22 isomer
C12H24 isoiner
^-dodecane
C13H26 isomer
trichlorobenzene isoroer
(traces)
C13H28 lsomer
unsat. hydrocarbon
CTOH^,- isomer
U zo
unsat. hydrocarbon
unsat. hydrocarbon
C13H26 isomer
C13H28 isomer
C,2^24 isomer
C.jH-g isomer
£-tridecane
sat. hydrocarbon (tent.)
sat. hydrocarbon + C,-alkyl
phenol isomer (tent.)
C14H30 is°mer
sat . hydrocarbon
C14H30 isomer
C14H28 isomer
ii-tetradecane
alkyl benzene +
unsat. hydrocarbon
C15H32 isomer
sat. hydrocarbon
77
-------
TABLE 23. ANALYSIS FOR PRIORITY POLLUTANTS IN AIR STREAM FROM GRIT CHAMBER
AT SOUTH BURLINGTON, NC MUNICIPAL TREATMENT PLANT
Priority pollutants
methyl bromide
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
1, 1, 2, 2-tetrachloroethane
toluene
ethylb enzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
1, 1, 2-t'richloroethane
ng/cartridge
ND
114 + 7
15 + 2
ND
188
21,963 + 8,316
548 + 72
4,468 + 668
ND
260 + 34
41,850 + 4,950
93 + 5
16,095 + 1,705
ND
54,000 + 9,000
ND
31,835 + 2,665
3,275 + 275
38
ND
88,500
ND
2a
ng/min/f t
ND
1,140 + 70
15 + 20
ND
1, 880
219,630 + 83,160
4,480 + 720
44,680 + 6,680
ND
2,600 + 340
418,500 + 49,500
930 + 50
160,950 + 17,050
ND
540,000 + 90,000
ND
318,350 + 26,650
32,750 + 2,750
380
ND
885,000
ND
LODb
J-JWJ-S
5
5-10
5-10
25-50
3
1-2
10
10
1-2
5-10
10
0.2-0.5
5-10
2-5
2
<40
0.1-1
4
2
2
5
3-5
™1 /% n / J / JT Aa
LOD « limit of detection;
sampled (1.0 £).
calculated from LOD's in Table 19 and volume air
78
-------
(yg quantities) for a number of the priority pollutants that were present
in the air stream. The reproducibility between the Tenax GC sampling
cartridges was in most cases better than HKL5%,
Table 24 presents the levels of priority pollutants in the air stream
from the aeration basin at South Burlington, NC municipal waste treatment
plant. Again many of the priority pollutants were detected; however, a
comparison of this data with the results from the raw wastewater indicates
a considerable decrease in the amount of priority pollutants even though the
air-stream rate from the wastewater was 'vlO £/min/ft2 in both cases. The
difference in concentrations between air streams from the raw wastewater and
activated sludge suggests that a considerable quantity of the priority
pollutants have been stripped by the air stream at the grit chamber (and by
removal at other points in the process) prior to entering the aeration basin.
Table 25 presents additional data on the emission rates of priority
pollutants from aeration of activated sludge at the Durham, NC treatment
plant. Again, many of the priority pollutants were detected in the air
stream at yg/min/ft2 amounts. Supporting data are given in Appendix A.
Samples from the vent of a pure oxygen (closed chamber) system were
taken at the Danville, VA municipal waste treatment plant. These results
are shown in Table 26. Many of the priority pollutants which were detected
in the samples taken at the South Burlington and Durham, NC plant were not
detected in these samples.
The detection limits using the determined limits.of detection from the
thermal desorption GC/MS/GOME of authentic compounds in combination with
sampling volumes employed at the various treatment plants are given in
Tables 24-26. The combined sampling and analysis method provided low ng/£
sensitivities. Furthermore, a sampling volume of 1 £ was optimum in these
cases (>3 H overloaded the analytical system) .
Table 27 presents the recovery of priority pollutants from activated
sludges which were purged using the designed sampler. In these experi-
ments, 7 H, of water was placed into a rectangular glass tank,, and the liquid
was purged with clean air (up to 14 £) and the entire air stream was direc-
ted through the designed sampler. In the first experiment, distilled water
was placed in the glass tank and purged with air to determine the back-
ground from the system (Table 27). Subsequently, activated sludge from the
Durham, NC plant was purged with air to determine the levels of priority
pollutants present in the wastewater, and then the wastewater was spiked
with increasing quantities of priority pollutants. Each time the waste-
water was purged, and total flow directed to the Nutech sampler. At the end
of the experiment, the glass tank was rinsed with distilled water ami th<=m
filled and purged to determine the background that might have occurred as a
"memory.effect" in the transfer line between the sampling head and the
sampler. The data in Table 27 indicate that no appreciable "memory effect"
was observed when the umbilical transfer line was maintained at 40°C, even
when sampling an air stream from the wastewater containing microgram quan-
tities of priority pollutants (Table 27). This series of experiments
indicated that the transfer line at 40°C minimizes the effect of adsorption
79
-------
TABLE 24. ESTIMATION OF PRIORITY POLLUTANT LEVELS IN AIR STREAM FROM
AERATION BASIN AT SOUTH BURLINGTON, NC MUNICIPAL WASTE
TREATMENT PLANT
Priority pollutants
methyl bromide
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
1,1,2, 2-tetrachloroethane
toluene
ethylbenzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
1,1, 2-trichloroethane
ng/cartridge
ND
117 + 1
ND
ND
75+7
3,472 + 205
320 + 23
487 + 35
ND
52 + 12
35,850 + 2,350
126 + 24
2,937 + 277
ND
19,300
ND
570
262
190
19
2,700
41,910
2a
ng/min/f t
ND
1,146 + 9.8
ND
ND
735 + 69
34,026 + 2009
3,136 + 225
4,773 + 343
ND
510 + 118
351,330 + 23,030
1,235 + 235
28,728 + 2,715
ND
189,140
ND
5,586
2,568
1,862
186
26,460
410,718
LODb
5
5-10
5-10
25-50
3
1-2
10
10
1-2
5-10
10
0.2-0.5
5-10
2-5
2
<40
0.1-1
4
2
2
5
3-5
a9.8 A/min/ft2
LOD - limit of detection;
sampled (1.0 &).
calculated from LOD's in Table 19 and volume air
80
-------
TABLE 25. ESTIMATION OF PRIORITY POLLUTANT EMISSIONS RATE FROM AERATION OF
ACTIVATED SLUDGE AT DURHAM, NC TREATMENT PLANT
Priority pollutants
methyl bromide
dichlorome thane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
1, 1, 2, 2-tetrachloroethane
toluene
ethylbenzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
1,1, 2-trichloroethane
ng/£
ND
1,972 + 85
ND
126
30 + 38
11,980 + 450
84 + 22
6,741 + 601
108
291 + 22
ND
2,519 + 12
4,934 + 175
ND
8,043 + 354
ND
49,771 + 4,416
814 + 86
41+4
3,451 + 384
54,032 + 7,152
ND
2a
ng/min/f t
ND
5,048
ND
322
756 + 97
30,669 + 1,152
215 + 56
17,257 + 1,539
276
744 + 56
ND
6,449 + 325
12,631 + 448
ND
20,590 + 906
ND
127,413 + 11,305
2,083 + 220
104 + 2
8,835 + 983
138,321 + 18,309
ND
LODb
(ng/A)
5
5-10
5-10
25-50
3
1-2
10
10
1-2
5-10
10
0.2-0.5
5-10
2-5
2
<40
0.1-1
4
2
2
5
3-5
a2.56 £/min/ft2
LOD = limit of detection;
sampled/aeration'rate.
calculated from LOD's in Table 19 and volume air
81
-------
TABLE 26. ESTIMATION OF PRIORITY POLLUTANT LEVELS IN VENT FROM PURE
OXYGEN (CLOSED CHAMBER) SYSTEM AT DANVILLE, VA
MUNICIPAL WASTE TREATMENT PLANT
Priority pollutant
methyl bromide
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1, 1, 1-trichloroethane
carbon tetrachloride
br omo dichlo rome thane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
toluene
ethylb enzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorob enzene
1,1, 2-trichloroethane
ng/cartridge
ND
331 + 97
ND
ND
ND
490 + 44
ND
26
ND
ND
ND
ND
138
ND
ND
371
T
ND
ND
141 + 16
940
ng/m
ND
233,098 + 68,309
ND
ND
ND
345,070 + 30,985
ND
18,309
ND
ND
ND
ND
97,183
ND
ND
261,267
T
ND
ND
99,296 + 11,268
66,971
LODa3
(ng/m )
3,448
3,448-6,896
3,448-6,896
17,241-34,000
2,069
690-1,379
6,900
6,900
690
3,448-6,900
6,900
137-344 '
3,448-6,900
1,379-3,448
1,379
69-690
2,759
2,759
1,379
1,379
2,069-3,448
- limit of detection; calculated from LOD's in Table 19 and volume of
air sampled.
82
-------
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of priority pollutants when sampling at high concentrations. The potential
for contamination of subsequent samples appeared to be extremely low.
84
-------
CHAPTER 10
ACCURACY AND PRECISION OF "PURGEABLE" PRIORITY POLLUTANT COLLECTION
AND STORAGE
INTRODUCTION
This section describes the quantitative capability of the developed
sampling and analysis technique. The objectives were to examine the reco-
very of purgeable radiotracer organics from organic-free water, raw waste-
water and activated sludge from a laboratory vessel. The distribution of
the radioactive pollutant between the liquid and gas phases was examined, as
well as the recoveries of organics from the gas phase by the Tenax GC samp-
ling cartridge.
Further studies were also conducted on the accuracy of sampling, utili-
zing the Nutech Model 851 sludge sampler, by examining the collection and
recovery of radiotracer "purgeable" priority pollutants added to the air-
stream from activated sludge. This.study served to determine the accuracy
of collection of priority pollutants during stripping of the municipal
and activated sludge waters.
Also, an assessment was made of the recovery of priority pollutants
from the Tenax GC sampling cartridge after a period of storage. The use of
radiotracer priority pollutants allowed the determination of mass-.balances in
the experiments.
EXPERIMENTAL
Recovery of Radiotracer Priority Pollutants From Aqueous Matrices
A series of radiotracer priority pollutants which were commercially
available were used for confirmation of recovery from aqueous matrices.
These are listed in Table 28. Priority pollutants were selected to cover a
range of volatility and solubility in water.
Experiments were performed by adding individual isotopes to: (1)
organic-free water; (2) raw wastewater, and (3) activated sludge in a labora-
tory vessel (Fig. 23). The aqueous matrix was purged using two parts of air
to one part of liquid (v/v). Listed in Table 28 are the quantities of
isotopes used and the disintegrations/minute (dpm) . The radiotracer com-
pound was purged from the aqueous matrices and collected on a Tenax GC
sampling cartridge which was previously described in Section 5. The reco-
very experiments were conducted in quintuplicate. The apparatus shown in
Figure 24 was used to investigate the llfC-labeled compound recovered from
85
-------
TABLE 28. QUANTITY OF RADIOLABELLED PRIORITY POLLUTANTS
USED IN RECOVERY EXPERIMENTS
Chemical
Quantity of isotope added
yg (dpm)
14
Chloroform- C
14
Carbon Tetrachloride- C
14
Benzene- C
14
Toluene- C
14
Chlorobenzene- C
14
Bromobenzene- C
23.0 (13.75 x 105)
6.0 (3.00 x 105)
10.8 (32.50 x 105)
12.0 (5.50 x 105)
2.9 (5.25 x 105)
5.0 (15.25 x 105)
86
-------
A
M TENAX CARTRIDGE
96 on
,40 mm ID
CLASS SINTERED
"FRIT
AIR
Figure 23. Vessel employed in radiolabeled priority pollutant studies.
87
-------
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the spiked matrices. Solutions of the llfC~labeled compound were dissolved
in methanol and added at levels of 5-40 ppb (^3-15 x 105 dpm) . The total
carrier volume (methanol) was 250 yl.
Table 29 presents the purging condition employed in this experiment.
After purge and trap was completed, the Tenax GC sampling cartridges were
thermally desorbed in the chamber (Fig. 24) for 10 min at 270°C with a purge
rate of 30 ml/min. The effluent gas was bubbled through 15 ml of Triton-X
scintillation counting fluid (cocktail) and 3 tandem scintillation vials
(Fig. 24). Each scintillation vial of the triplicate series was indivi-
dually counted on a Packard Tricarb 3375 liquid scintillation spectrometer
to determine the total radioactivity recovered by thermal desorption of the
Tenax GC cartridge. Also breakthrough of radioactivity was determined
between the first, second or third tandemly arranged scintillation vials
(Fig. 24). The radiotracer sample was counted until a standard error of 2.5
was obtained. The scintillation fluid was 6.0 g Omnifluor (New England
Nuclear, Boston, MA) per liter of toluene. Observed radioactivity was
corrected for quenching by the external standard ratio method and all counts
were converted to dpm.
Standards for each radiotracer priority pollutant were prepared in quin-
tuplicate by injecting with a Lambda (§) pipette (250 yl; this pipette was
used for loading all aqueous matrices) directly into the counting vial
containing 15 ml of Triton-X cocktail. The percent of compound recovery was
calculated as follows: recovered = (dpm found in first + second + third
scintillation vial) * (average dpm found in the standard x (100). The trapping
efficiency for 15 ml of Triton-X cocktail in the first vial was determined, as
well as for the second vial, to ensure that breakthroueh had not oor.urrp.rl,
The possibility of breakthrough of compounds from the Tenax GC cartridge
during the purge and trap of the 1IfC-labeled spiked aqueous matrix was also
investigated by using a second cartridge.which was placed in tandem behind
the first Tenax cartridge. Each was individually thermally desorbed into
three fresh vials of Triton-X cocktail. Thus, the amount of radioactivity
appearing on the second backup cartridge was determined. No radioactivity
appeared in the backup Tenax GC cartridge for any of the priority pollutants
studied.
Accuracy of Sampling
The accuracy and reproducibility of trapping priority pollutants from
an air stream leaving activated sludge and municipal wastewater onto Tenax
GC sampling cartridge was studied. The efficiency of transfer of priority
pollutants through the transfer line of the model 851 sampler was determined,
and the potential memory effects which might occur within the transfer line
between sampling periods was assessed.
The sampler under evaluation was shown in Figure 18. A schematic
diagram of the pneumatic was also shown in Figure 25. Triplicate Tenax GC
sampling cartridges with backup cartridges were used to determine accuracy
and precision. Six liters of activated sludge from the Northside Treatment
Facility in Durham, NC was placed in a 9 £ glass vessel and purged using the
parameters described in Table 30. Upon initiating the purging of activated
89
-------
TABLE 29. PARAMETERS USED FOR RECOVERY EFFICIENCY STUDIES OF
PRIORITY POLLUTANTS, SIMULATING MUNICIPAL TREATMENT
FACILITY OPERATIONS
Parameter
Set point
Liquid Volume Purged
Air Volume Purged
Purge Rate
Time
Volume of Isotope + Carried Added
400 ml
800 ml
100 ml/min
8 min
250 \ii
90
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91
-------
TABLE 30. PARAMETERS USED FOR DETERMINING SAMPLING PRECISION,
ACCURACY, AND "MEMORY EFFECT"
Parameters
Condition
Volume activated sludge purged
Purge rate
Purge volume
Transfer line temperature
Sampling rate/cartridge
(performed in triplicate)
Sampling time
No. of tandem Tenax cartridges
1.2 Upm
12 H
40°C
300 m£/min
10 min
2
92
-------
sludge at a rate of 1.2 &/minute, the radiotracer priority pollutant was
injected into the heated umbilical transfer line (Table 31) and sampling was
conducted at a rate of 300 ml/minute/cartridge. Sampling was continued for
10 min. After sampling was completed, the cartridges were replaced with an
unexposed set and the transfer line was further purged for 10 additional
minutes with a clean air supply, prior to the next collect to be perfor-
med. In each case when the experiment was repeated, fresh activated sludge
from the aeration pond was also placed in the glass purging vessel. Experi-
ments were performed in duplicate to determine accuracy and precision for
each priority pollutant.
Radiotracer priority pollutants were recovered by thermally desorbing
the radiolabeled compound from the Tenax GC sampling cartridge into the
Triton-X scintillation cocktail (Fig. 24). Determination of dpm was con-
tinued until a standard error of 2.5% was achieved for each radioactive
sample. The sampling accuracy was calculated by ratioing the observed
radioactivity on the front and backup Tenax cartridges to the amount of
radioactive priority pollutant injected into the umbilical transfer line.
The fraction of the total sample which was collected by each Tenax GC cart-
ridge was taken into account for each of the three replicates. Reproduci-
bility of sampling was calculated as an average for the three front cart-
ridges and three backup cartridges.
An investigation was conducted of the potential "memory effects" of
priority pollutants occurring in the heated transfer line as a result of
sampling airstreams spiked with radiotracer priority pollutants. After
completing the sampling the transfer line was purged with 12 H of clean air
and the radioactivity in the line was determined by sampling the air passing
through the transfer line with fresh Tenax GC cartridges (subsequent to each
of the experiments for determining sampling precision and accuracy).
Sample Storage Study
The recovery of priority pollutant (from stored Tenax samples) from the
airstream passing from the activated sludge aeration basin was performed
using a Nutech 851 sampler. A total of 16 replicate cartridges were col-
lected with five blanks serving as controls. The priority pollutants
present in the aeration gases were determined by GC/MS/COMP techniques as
described in Section 8 and for those priority pollutants which were detec-
ted, each one was quantified at intervals over a three-week period. Ini-
tially, the day after sampling was completed, the priority pollutant con-
centration was determined and then again at 1, 2 and 3-week intervals. Each
analysis was conducted in triplicate. Samples were stored at -20°C.
RESULTS AND DISCUSSION
Recovery of Radiotracer Priority Pollutants From Aqueous Matrices
Table 32 presents the recovery of the radiotracer priority pollutants
from distilled water (organic free)., raw wastewater and activated sludge
from the Northside Treatment Facility in Durham, NC. The values are given
as the average percent of five determinations with corresponding standard
deviation.
93
-------
TABLE 31. LEVELS OF PRIORITY POLLUTANTS ADDED TO AIR STREAM
FROM ACTIVATED SLUDGE3
Priority pollutant
Quantity used (ng)
Methyl bromide
Chloroform
Carbon tetrachloride
Benzene
Toluene
Chlorobenzene
Bromobenzene
1,050
460
60
215
240
57
100
12 & of air was purged through 6 & of activated sludge.
94
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The coefficient of variation is in parenthesis. For the six radioisotopi-
cally labeled priority pollutants virtually little variation was observed
among organic-free water, raw wastewater and activated sludge. However,
these recoveries are somewhat lower than those obtained with the purge-and-
trap vessels employed for priority pollutant analysis. This is expected
since the ratio between the volume of gas purged through the aqueous matrix
and the volume of aqueous matrix is considerably lower than that employed in
the standard purge-andjtrap devices.
Sampling Precision and Accuracy
Table 33 presents -the sampling precision for selected priority pollu-
tants using Tenax GC sampling cartridges. For all priority pollutants
studied, the sampling precision for the compounds was at least within +10%.
The collection efficiency was essentially quantitative for the first Tenax
cartridge in the sampling train as determined by the amount of priority
pollutants distributed between the front and backup Tenax cartridge.
Table 34 presents the sampling accuracy for a few priority pollutants
using these sampling devices. For the compounds studied, quantitative
recoveries were observed except for bromobenzene, which because of its lower
vapor pressure was partially trapped on the aerosol filter.
The memory effect contribution in the sampler transfer line from samp-
ling airstream containing priority pollutants was also examined. After
completing the collection of each priority pollutant to determine the
sampling accuracy and precision, the transfer line was further purged with
clean air for a total of 10 min (12 £), and then the background of the
transfer line was determined. These results are given in Table 35. Indi-
cated are the total radioactivity (dpm) sampled in the previous experiments
and the dpm observed after purging of the sampler transfer line. In all
cases, the percent memory effect was <0.2%.
The data presented in Tables 33-35 indicate that the Tenax sampling
cartridge provides quantitative collection of priority pollutants in air-
streams leaving grit chambers and activated sludge aeration basins. Fur-
thermore, cross contamination of samples from one sampling period to the
next is essentially negligible with this sampling system.
Sample Storage Study
A study was performed to determine the recovery of priority pollutants
from stored Tenax samples collected from the airstream of an activated
sludge aeration basin. The results of the recovery study are given in Table
36. The data represent the means and standard deviations for triplicate
analyses with values in ng/3 & of sample volume. Also included is the
subsequent percent recovery (given in parenthesis) which was taken as 100%
for the initial determination (day 1).
The recovery of chloroform decreased from 100% to 50% after three weeks
of storage. For the remaining priority pollutants which were detected in
these samples, the recovery was essentially quantitative after three weeks of
96
-------
TABLE 33. SAMPLING PRECISION AND COLLECTION EFFICIENCY FOR SELECTED PRIORITY
POLLUTANTS USING TENAX GC SAMPLING CARTRIDGES
Expt. No. la
Priority pollutant
Methyl bromide
Chloroform
Carbon tetrachloride
Benzene
Toluene
Chlorobenzene
Bromobenzene
Each experiment was
Front
62 + 6
93 + 2
77 + 13
95 + 3
93 + 2
86 + 1
80 + 6
conducted using
Back
37 + 4
7 + 3
23 + 10
5 + 4
7 + 2
14 + 1
20 + 9
triplicate
Expt. No. 2
Front
-
98 + 3
92 + 1
98 + 0
94+2
83 + 17
75 + 2
cartridge sets (front
Back
-
7 + 4
18 + 1
2 + 0
6 + 2
15 + 15
25 + 3
and
97
-------
TABLE 34. SAMPLING ACCURACY FOR SELECTED PRIORITY POLLUTANTS USING
TENAX GC SAMPLING CARTRIDGES
Priority pollutant
Chloroform
Carbon tetrachloride
Benzene
Chlorobenzene
Bromobenzene
3.
Expt. no. 1
119 + 27
78 + 22
87 + 25
96 + 10
50 + 22
Expt. no. 2
106 + 25
80 + 5
94 + 3
104 + 14
55 + 10
aEach experiment was conducted in triplicate, values are in percent of
value with + S.D.
98
-------
TABLE 35. "MEMORY EFFECT" CONTRIBUTION IN SAMPLER TRANSFER
LINE FROM SAMPLING AIR STREAMS CONTAINING PRIORITY POLLUTANTS
Priority pollutant
Methyl bromide
Chloroform
Carbon tetrachloride
Benzene
Toluene
Chlorobenzene
Bromobenzene
Total dpma
sampled (ng)
1.
5.
1.
1.
2.
2.
6.
5 x
5 x
2 x
3 x
2 x
1 x
1 x
105
io5
io5
IO5
io4
IO4
IO4
(1,050)
(460)
(60)
(215)
(240)
(57)
(100)
Residual dpm
observed
144
166
276
130
45
29
114
Percent
"memory"
0.08
0
0
0
0
0
0
.03
.23
.01
.20
.14
.19
Represents total radioactivity and mass of priority pollutant sampled through
line, followed by a 12-liter purge with clean air and then checked for
residual radioactivity in transfer line.
99
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storage at -20°C. As the volatility of the priority pollutants decreased,
the corresponding recovery improved (the standard deviation also decreased)
For priority pollutants which were detected at trace levels immediately
after sampling, they were also detectable in trace quantities after three
weeks storage.
During the GC/MS/COMP analysis, a search was made for all of the
priority pollutants which might be considered as "purgeable" in these sam-
ples. However only those given in Table 36 were found.
The accuracy and precision of collecting, storing and analysis of
purgeable priority pollutants are satisfactory for the purpose of designa-
ting this procedure as a quantitative method.
102
-------
REFERENCES
1. Metcalf and Eddy, Inc., "Wastewater Engineering: Collection, Treatment,
Disposal." McGraw-Hill Book Company, New York 1972.
2. "Aeration in Wastewater Treatment, Manual of Practice No. 5," Water
Pollution Control Federation, Washington, DC 1971.
3. "Operation of Wastewater Treatment Plants. Manual of Practice No. 11,"
Water Pollution Control Federation, Washington, DC 1976.
4. Fair, G. M., Geyer, J. C. and Okun, D. A. "Water and Wastewater Engi-
neering," Vol. 2, "Water Purification and Wastewater Treatment and
Disposal," John Wiley & Sons, Inc., New York 1968.
5. Pellizzari, E. D., "Development of Method for Carcinogenic Vapor Analy-
sis in Ambient Atmospheres." Publication No. EPA 650/2-74-121, Contract
No. 68-02-1228, July 1974. 148 pp.
6. Pellizzari, E. D., "Development of Analytical .Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors." Publication No. EPA-600/2-75-
075, Contract No. 68-02-1228, November 1975. 187 pp.
7. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal. Lett.,
9f 45 1976.
8. Pellizzari, E., "Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy." Publication No. EPA-600/2-77-100, June
1977. 104 pp.
9. Pellizzari, E. D., "The Measurement of Carcinogenic Vapors in Ambient
Atmospheres." Publication No. EPA-600/7-77-055, Contract No. 68-02-
1228, June 1977. 288 pp.
10. Pellizzari, E., "Measurement of Carcinogenic Vapors in Ambient Atmos-
pheres." EPA Contract No. 68-02-1228, 1978. in press.
11. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch and E. Sawicki,
Environ. Sci. Tech., j^, 556 1975.
12. Pellizzari, E. D., "Improvement of Methodologies for the Collection and
Analysis of Carcinogenic Vapors." EPA Contract No. 68-02-2764, 1978.
in press.
103
-------
13. Pellizzari, E. D., "Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy," EPA Contract No. 68-02-2262, 1978. in
press.
14. Bishop, F., EPA-Cincinnati Laboratory, private communication.
15. "Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants", U. S. E. P. A., Cincinnati, OH, April 1977.
134 pp.
104
-------
APPENDIX A
VOLATILE ORGANICS IN AIR STREAM FROM GRIT CHAMBER
Figure Al. Reconstructed GC/MS chromatogram of volatile organics
in air stream from grit chamber at S. Burlington, NC
Treatment plant (Sample 1, 1.0 £).
105
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APPENDIX B
VOLATILE ORGANICS IN AIR STREAM FROM AERATION POND
- TIC» 5
Figure Bl. Reconstructed gc/ms chromatogram of volatile organics
in air stream from aeration pond at S. Burlington,
NC Treatment Plant (Sample 1, 1.0 £).
142
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tfl
g cu
cfl 5-1
M J-"
bO
O U
cfl
CU CO
4-1 tfl
S-l fl
4J O
.CO »H
C3 W
O Cfl
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CU CU
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IO
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166
-------
APPENDIX C
VOLATILE ORGANICS IN VENT FROM PURE OXYGEN (CLOSED CHAMBER) SYSTEM
ee.e-
tg 20.8-
lee.e
86. e
01
u
c
- TIC* 5
20 25
Time (min)
01
•H
JS 2C.O-
1
6 5 18 15 20 25 30
Time (min)
' ' ' 'ss ' ' ' ' ' ' ' ' ~
- TIC* S
Figure Cl. Reconstructed GC/MS chromatograms for volatile organics
in vent of closed chamber at Danville, VA Treatment
Plant.
167
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i
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168
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169
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(BUI
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170
-------
APPENDIX D
ANALYSIS OF PRIORITY POLLUTANTS IN AIRSTREAMS FROM
WASTEWATER AND ACTIVATED SLUDGE >
110 SCOPE AND APPLICATION
111 This method covers the determination of volatile priority pollu-
tants which are stripped into the air streams passing through raw
wastewaters and activated sludge. The organics are adsorbed from
the air onto a Tenax GC sampling cartridge (1). Recovery of the
volatile priority pollutants is accomplished by thermal desorption,
purging with helium into a liquid nitrogen cooled nickel capillary
trap (2-6), and introducing the vapors into a gas chromatographic
column where they are separated from each other (1). The charac-
terization and quantification of the priority pollutants are
accomplished by a mass spectrometry (1).
112 This method is applicable for the estimation of levels of "vola-
tile" priority pollutants purged from raw and municipal waste-
waters by process aeration. It can be used to monitor these
compounds with anticipated limits of detection between 1 ng/5,
(§.•.£•> chlorobenzene) and 90 ng/£ (e_.&., 1,2-dichloropropane) in
air for screening survey's of municipal wastewater treatment
plants.
120 SUMMARY
121 This method offers considerable analytical versitility since a gas
chromatograph/mass spectrometer/computer system is used for the
analysis. Interfaced with a glass jet separator, the GC/MS/COMP
system is extremely sensitive and specific for the analysis of
"volatile" priority pollutants in the air stream from wastewaters
at municipal sewage treatment plants. The combined use of a gas
chromatographic column and specific or unique ions (m/z) repre-
senting the various compounds of interest provides a relatively
specific assay method for these priority pollutants (1). The
procedure describes a sampling system for air streams passed
through raw wastewaters and activated sludge (open and closed
basins), a thermal desorption unit, GC/MS/COMP operating para-
meters and methods for quantification.
122 Collected samples can be stored up to approximately 3 weeks with
recoveries of priority pollutants typical of those shown in
Table Dl. Because some of the compounds of interest may be
171
-------
TABLE Dl. RECOVERY OF PRIORITY POLLUTANTS FROM STORED TENAX CARTRIDGES
Priority pollutant
1, 1-dichloroethylene
1, 2-trans-dichloroethyleiie
1,1, 1-trichloroethane
1, 2-dichloroethane
trichloroethylene
1, 2-dichloropropane
tetrachloroethylene
chlorobenzene
bis- (2-chloroethyl) ether
bis- (chloromethyl) ether
acrolein
acrylonitrile
benzene
toluene
ethy Ib enzene
chlorobenzene
1, 1-dichloroethane
bromodichloromethane
bromoform
Percent
14 da
48 + 12
73+9
92 + 2
100 + 7
99 + 9
86 + 4
97+3
80+7
86 + 6
41 + 4
45 + 15
ND
104 + 8
103 + 3
61+9
80+7
102
106
79
recovery
21 da
35 + 8
99 + 12
NDa
122 + 9
87 + 13
ND
68 + 3
87 + 3
93
ND
49 + 6
81+6
104
103 + 7
65 + 11
80 + 4
90
77
ND
I$D s not determined.
172
-------
hazardous to man, it is extremely important to exercise safety
„ precautions in the preparation and disposal of liquid and gas
standards, cleaning of used glassware, etc.
123 This method is recommended for use only by experienced sampling
personnel and GC/MS/COMP analysts or under the close supervision
of such qualified persons.
130 APPARATUS AND REAGENTS
131 For sampling protocol
131.1 Pyrex glass tubes - 1.5 cm i.d. x 10 cm in length
131.2 Tenax GC (35/60 mesh)
131.3 Silanized glass wool
131.4 Calcium sulfate (anhydrous)
/T?\
131.5 Kimax^-'(2.5 cm x 1.57 cm) culture tubes
131.6 Aluminum foil and teflon-lined caps for 131.5
131.7 One gallon paint cans or equivalent
131.8 Tweezer
131.9 Kimwipes ^ , gum labels
132 For cartridge preparation
132.1 High purity helium gas
132.2 Clean-up solvents: (a) methanol; (b) n-pentane-both
glass redistilled
132.3 Muffle furnance (range to 600°C)
132.4 Thermal desorption unit (Nutech Model 321 or equivalent)
132.5 Soxhlet apparatus
132.6 Vacuum oven
133.7 Stainless steel sieves (35/60)
133 For sampling
133.1 Nutech 221-1A sampler (Durham, NC: or equivalent)
173
-------
133.2 Pyrex glass tube (Nutech 320-3-101 or equivalent - 1.5 cm
i.d. x 10 cm in length)
133.3 TFE coupling (Nutech 320-3-102)
133.4 Aerosol prefilter (Nutech 320-3-104)
133.5 Quick connect (Nutech 320-3-103)
133.6 Teflon filters - 0.2 y porosity, Gelman (2.5 cm diameter)
133.7 Aeration tank sampler - parts listed in Table D2, see
Figures D1-D4 (Nutech Model 851 or equivalent)
134 For quantitation
134.1 Gas chromatograph/mass spectrometer/computer system (cap-
able of performing functions under 170)
134.2 Gas chromatographic column materials: (a) 8 ft stainless
steel x 0.1 in i.d. tube packed with Carbopak C (60/80
mesh) coated with 0.2% Carbowax 1500; (b) 1 ft stainless
x 0.1 in i.d. column packed with Chromosorb W coated with
3% Carbowax 1500
134.3 Permeation tubes (see Table D3)
134.4 Permeation apparatus (see Figure D5)
134.5 Syringes - 10 yA volume, additional sizes may also be
required
140 PREPARATION OF SAMPLING CARTRIDGES
141 Calcium sulfate is cleaned and dehydrated in a muffle furnace at
500°C for 4 hrs, cooled and kept under an argon atmosphere. -^
Approximately 1 g CaSOi^ is placed at the bottom of the Kimax ^
sample transport tube and covered with about 2 cm of pyrex wool.
Anhydrous CaSO^ is used to dry the sampling cartridges after
sampling "humid" air streams and the CaSO^ is retained in the
sample transport tubes throughout the entire storage period.
142 Virgin Tenax GC (Applied Science, State College, PA, or material
to be recycled) is extracted in a Soxhlet apparatus for a minimum
of 18 hrs each time with methanol and n-pentane prior to prepara-
tion of cartridge sampling tubes (Nutech Corp., Durham, NC).
After purification of the Tenax GC sorbent and drying in a vacuum
(^28 in H20) oven at 100°C for 3-5 hrs, the sorbent is meshed to
provide a 35/60 particle size range. This operation should be
carried out in an atmosphere which is free of organic vapor
background.
174
-------
TABLE D2. PARTS LIST FOR AERATION TANK SAMPLER
Nutech part #a
851-001
851-002
851-003
851-004
851-005
851-006
851-007
851-008
851-009
851-010
851-011
851-012
851-013
851-014
851-015
851-016
851-017
851-018
851-019
851-020
851-021
851-022
851-023
851-024
851-025
851-026
851-027
851-028
851-029
851-030
Description
cabinet enclosure #201-002
sample chamber #320-001
stainless sample hood
polyethylene foam pad
heated TFE sample line
quick connect, 1/2" female
quick connect, 1/2" male
thermocouple, type K
dry gas meter w/ thermometer installed
mass flow meter
24 VDC power supply
diaphragm pump
temperature control board
relay w/ socket, 110 VAC, DP
4 terminal barrier strip
switch SPST
fuse holder
LCD display
power cord
male AC connector
female AC connector
switch DPDT
valve, flow control
valve, solenoid, 110 VAC
stainless manifold, 4 port
stainless manifold, 5 port
check valve
cartridge assembly w/TFE union
sample manifold, 3 port TFE
1/4 NPT nipple, TFE
Quantity
1
1
1
4
1
1
1
1
#221-028 1
1
1
1
1
1
2
2
2
1
1
1
1
1
3
3
1
1
1
3
1
3
(continued)
175
-------
TABLE D2 (cont'd.)
Nutech part #
851-031
851-032
851-033
851-034
851-035
851-036
851-037
851-038
851-039
851-040
851-041
851-042
851-043
851-044
851-045
851-046
851-047
851-048
851-049
851-050
851-051
851-052
851-053
851-054
851-055
Description
bulkhead union, 1/4"
stainless L
TFE reducer 1/2" to 7/16"
hose clamp, 7/16"
switch SPST
indicator lamp
1" foam insulation
piano hinge, 8"
deleted
screws, misc.
house coupling, 1/2 NPT
pot, IK, 20T
resistor 1%, 8.2K
thermocouple connector, male, type K
thermocouple connector, female, type K
thermocouple connector, mounting bracket
fuse, 2A
fuse, 3A
crimp terminal
vinyl tubing 3/16 x 5/16"
vinyl tubing 7/16 x 5/8"
cabinet base #201-001
control panel #201-004
cabinet handles #201-008
knockout jar
Quantity
3
3
1
1
3
1
2ft2
1
17
1
1
1
1
1
1
1
30
15 ft
3 ft
1
1
3
1
or its equivalent.
176
-------
DIGITAL DISPLAY-
TEMP/MASS FLOW
READOUT SWITCH
POWER AND PUMP
SWITCHES
CONTROL CONSOLE
SOLENOID VALVE
SWITCHES
METERING VALVES
DRY GAS METER
Figure Dl. Schematic of sampler system for grit chambers and aeration
tanks.
177
-------
r
o
M
CO
too
o
•H
4-1
o
CO
CM
O
00
•rt
178
-------
HEADED UMBILICAL
CARTRIDGE MANIFOLD
EXHAUST
CHECK i
VALVE
-------
irov
PUMP
A_n_rLn—
CARTRIDGE CHAMBER HEATER
SOLENOID VALVES
Figure D4. Schematic of electronics in sampler system.
180
-------
TABLE D3. PERMEATION TUBES FOR SEVERAL VOLATILE PRIORITY POLLUTANTS (1)
Priority pollutant
methyl choride
dichlorodifluoromethane
methylbromide
vinyl chloride
chloroethane
dichlorome thane
trichlorof luoromethane
1,1-dichloroethylene
1 , 1-dichloroethane
1, 2-trans-dichloroethylene
chloroform
1 , 2-dichloroethane
1,1, 1-tri chloroethane
carbon tetrachloride
bromodichloromethane
bis-(chloromethyl) ether
1 , 2-dichlor opropane
1, 3-trans-dichloropropane
trichloroethylene
dibromochloromethane
1,3— cis-dichloropropene
1,1, 2-trichloroethane
benzene
2-chloroethylvinyl ether
bromoform
1,1,2, 2-tetrachloroethene
1,1,2, 2-tetrachloroe thane
toluene
chlorobenzene
ethyl benzene
acrolein
acrylonitrile
bis-(2-chloroethyl) ether
perfluoro toluene
1 , 3-dichlorobenzene
perfluorobenzene
Permeation tube
Dimensions
(O.D. x I.D. x length, cm)
0.64 x 0.48 x 6.5
Unknown
0.64 x 0.48 x 6.0
0.64 x 0.48 x 10.0
Unknown
0.64 x 0.48 x 11.0
Unknown
0.64 x 0.48 x 10.1
0.64 x 0.48 x 9.9
0.64 x 0.48 x 10.0
0.64 x 0.48 x 11.0
0.64 x 0.48 x 8.0
0.64 x 0.48 x 8.0 '
0.64 x 0.48 x 9.9
0.64 x 0.48 x 5.2
Unknown
0.64 x 0.48 x 7.7
Unknown
0.64 x 0.48 x 10.0
Unknown
Unknown
0.64 x 0.48 x 10.3
0.64 x 0.32 x 0.6
Unknown
0.64 x 0.48 x 5.1
0.64 x 0.48 x 5.2
0.64 x 0.32 x 7.0
0.64 x 0.48 x 7.0
0.64 x 0.48 x 5.5
0.64 x 0.48 x 12.7
0.64 x 0.48 x 10.0
0.64 x 0.48 x 10.4
0.64 x 0.48 x 8.3
0.64 x 0.48 x 7.2
0.64 x 0.32 x 9.0
0.64 x 0.48 x 5.5
Material
FEP
FEP
FEP
FEP
TFE
TFE
TFE
FEP
TFE
TFE
TFE
TFE
TFE
TFE
TFE
PE
PE
TFE
PE
TFE
TFE
TFE
TFE
TFE
TFE
FEP
PE
FEP
Approximate rate
g/min
1.8 x 10~6
1.2 x 10~6
2.0 x 10~6
7.0 x 10~7
1.0 x 10~6
4.2 x 10~7
1.1 x Hf5
6.4 x 10~8
4.0 x 10~7
9.1 x 10~8
3.0 x 10~8
1.1 x 10~7
9.8 x 10~8
2.2 x 10~6
6.2 x 10~8
7.1 x 10~6
2.5 x 10~5
3.6 x 10~7
9.7 x 10~6
1.9 x 10~7
2.0 x 10~7
6.8 x 10~8
1.3 x 10~6
1.0 x 10~6
1.0 x ID"10
8.94 x 10~6
1.1 x 10~7
8.5 x 10~6
181
-------
3-woj TEFLON-PLUG
STOPCOCKS
NEEDLE VALVES
MIXING CHAMBER
PERMEATION CHAMBER
JACKET
THERMOSTAT, HEATER , AND
CIRCULATING PUMP
CARRIER GAS LINES
THERMOSTAT FLUID LINES
Figure D5. Permeation system for generating air/vapor mixtures (1).
182
-------
143 Sampling tubes are prepared by packing in a 10 cm long x 1.5 cm
i.d. glass tube 6 cm of 35/60 mesh Tenax GC with glass wool in the
ends to provide support (1). Cartridge samplers are then con-
ditioned at 270°C with helium flow at 30 ml/min for 1 hr. The
conditioned cartridges are transferred to Kimax ® (2.5 cm x 150
cm) culture tubes (or Nutech sample cartridge transport tubes,
Fig. D6), packed with glass wool to prevent breakage, immediately
sealed using Teflon-lined caps (with no adhesive binders) and
cooled. Culture tubes containing the cartridges are immediately
placed in a metal container (equivalent to a paint can) which has
a pressure scalable cap. This procedure is performed in order to
avoid recontamination of the sorbent bed (1,6,7). The sampling
cartridges can be stored under these conditions for a period of
about 3 wks prior to sampling.
150 SAMPLING AND PRESERVATION
151 Integrated sampling of the air stream passing through wastewaters
at municipal treatment plants is accomplished using a prototype
Nutech Model 851 or equivalent sampler (Nutech Corp., Durham, NC).
Flow rate regulation between 5-300 ml/min is necessary. Flow
rates are maintained at prescribed rates using variable critical
orifices for the three sampling cartridges. The individual or
total flow through the cartridges is monitored with a calibrated
mass flow meter. The total flow from the aeration basin (minus
the sampling volume) is registered by a dry gas meter; only a
fraction (up to 30%) of the air stream passing through the samp-
ling unit is sampled by the Tenax GC cartridges.
151.1 Figure Dl depicts the sampling unit. The sampling unit con-
sists of a gas sampling head, a sample transfer line and a
gas sampling manifold. A Teflon ® manifold is used to
distribute the air stream to three replicate Tenax GC
cartridges; the remaining gas flow is measured with a dry
gas meter (Fig. Dl). The sampling cartridges are housed
in a constant temperature bath (70°F) in order to ensure
uniform and constant breakthrough volumes for the priority
pollutants throughout the entire sampling period.
151.2 The sampling head (Fig. D2) is constructed of 316 stainless
steel for corrosion resistance. The sampling area is
approximately 1 ft2 (4 in x 36 in). Internal baffles
inhibit entry of fluid into the transfer line (Fig. D2).
During operation, -bubbles rising from aeration pipes are
trapped in a closely defined shroud designed to maintain
an accurate sample area. The shroud is 16 gauge stain-
less steel so that only those bubbles rising within the
defined area are collected. Once trapped in the shroud,
the bubbles create a positive gas pressure forcing the
gases through the heated transfer line (40°C) to the
sampler.
183
-------
I
-Pfyenof/'c cap wtfh TFE
fi'necl sili'cone seal
320-3-302
-El cm g/ass
32O-3- 301
'1.3cm. TFEspacer
320-3-303
.-^•-.
-
( A
/
( y
- \, ., tyr ,. ^-, .„
TTtp/TT
•'-"----
J
•' y
G.C. Cartridge, 320-3-101
Figure D6. Sampler cartridge transport tube (Nutech Corp.,
Durham, NC).
184
-------
151.3 For typical operating conditions in open grit chambers and
activated sludge ponds, the gas sampling head is placed on
the wastewater which is supported by a flotation collar and
held in a fixed position by the support arms fastened to
guardrails. For some aeration rates through the activated
sludge, the gas flow is approximately 2.5 £/min/ft2 surface
area. This rate can be highly variable; however, it can be
easily determined prior to sampling by simply passing the
total flow through the dry gas meter for a short period of
time (M.O min) .
151.4 In general, a sampling volume of 1 ^./cartridge is suffi-
cient for achieving 1 ppb sensitivity. Thus, the sampling
rate is adjusted to accommodate the desired sampling period.
Triplicate cartridges are deployed on each sampling unit.
151.5 Larger volumes may be taken; however, the quantity of pol-
lutants accumulated on the sampling cartridges may ultima-
tely saturate the GC/MS/COMP system. For larger sample
volumes, it is important to realize that the total volume of
air sampled may cause the elution of a few of the priority
pollutants possessing low breakthrough volumes (Table D4).
These breakthrough volumes have been determined by a pre-
viously described technique (8). The breakthrough volume
has been defined as that volume which causes 50% of a
discrete sample introduced into the cartridge to pass
through the cartridge and be lost.
152 Continuous sampling for priority pollutants in the vents from
closed chambers is accomplished using a Nutech Model 221-1A port-
able '.sampler of equivalent (Nutech Corp.., Durham, NC; Fig. D7).
Flow rates between 10-300 ml/min are available with this sampling
system when using critical orifices. The total flow is monitored
through a calibrated flow meter to integrate the flow sampled from
all cartridges. The portable sampling unit operates on a 12 v
storage battery and is capable of continuous operation for a
period of 24 hr. However, in most cases at the rates which are
employed for sampling of the vent gas from the closed chambers,
the sampling period may be adjusted between 10 min and 3 hr.
Replicate cartridges may be deployed on each sampling unit utili-
zing a sampling head or manifold. The sampling head should be
connected to a vacuum line of approximately 20 ft so that the sam-
pler can be positioned at a distant location from the vent gas
unless the sampler itself is made.explosion-proof. The suggested
sample volume is 1 £ as described under 151.3. Larger sample
volumes may be taken if desired while considering breakthrough
volumes given in Table D4.
153 All Tenax GC sampling cartridges once prepared for field sampling
must be kept tightly closed in a double container as described
earlier (143). At the point when sampling is to begin, they are
185
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186
-------
POWER SWITCH
VALVE
VAC
FLOW METER
GAS VOLUME
REMOVABLE FRONT
AND REAR PANELS
BATT. TERMINAL
AC SWITCH
tZVOC(AUXILUARY)
^ 'U 1IAM8- '
gR
@^
GAS
METEP
\
t
Figure D7. Sampler schematic for closed chamber systems.
187
-------
to be removed from their respective containers and handled with
Kimwipes ® . After sampling is completed, the cartridges are
returned immediately to their containers, and coded on the label
which is affixed to the container. Samples are stored at -20°C
in sealed paint cans until ready for analysis. Experiments have
been conducted which demonstrate that the priority pollutant
vapors collected on Tenax GC sorbent are stable and can be quanti-
tatively recovered from the cartridge samplers up to 3 weeks after
sampling when they are tightly closed in sample cartridge holders
and placed in a second container that can be sealed, protected
from light and stored at -20°C (1).
160 REMOVAL OF INTERFERENCES
161 At the present time there are no known interferences using the
described collection and analysis system (1). The use of the
specified packed gas chromatographic column in combination with
single ion (m/jz) plots provides sufficient specificity for the
direct analysis of "volatile" priority pollutants on the Tenax GC
cartridges without further purification.
170 QUANTISATION
171 For quantitative measurements this method requires a gas chroma-
tography/mass spectrometer/computer.
171.1 The operation of the GC/MS/COMP system typically requires
the mass spectrometer to be first set to operate in the
repetitive scanning mode. In this mode the magnetic sec-
tor or quadrupole is automatically scanned upward from a
preset low mass to a high mass value. Although the scan
range may be varied depending on the particular sample,
typically the range is set from m/jz 25 to m/_z 300. The
scan is completed in approximately 1.0 sec. At this time
the instrument automatically resets itself to the low mass
position in preparation for the next scan, and the informa-
tion is accumulated by an on-line dedicated computer and
written onto either a disk or magnetic tape. The scan plus
reset period should be approximately 2.0 sec/scan cycle,
and repetitively executed throughout the chromatographic
run. The results are the accumulation of a continuous
series of mass spectra throughout the chromatographic run
in a sequential fashion.
171.2 Prior to running unknown samples, the system is calibrated
daily by introducing a standard substance perfluorokero-
sene (magnetic sector) or heptacosafluorotributylamine
(quadrupole) into the instrument. The calibration curve
which is thus generated is stored in the computer memory.
This calibration serves only to calibrate the masses over
the mass scanning range.
188
-------
172
173
174
175
The preparation of standards is required for calibrating the GC/
MS/COMP system for quantitative analysis of priority pollutants.
It is necessary to accurately spike Tenax GC sampling cartridges
with known amounts of priority pollutants and the internal stan-
dards, perfluorobenzene and perfluorotoluene, utilizing the
permeation system described earlier.
The permeation tubes must be gravimetrically calibrated (1,5,6,8).
In general, 500-1,000 ng of each priority pollutant is spiked onto
the Tenax GC cartridge along with a known quantity of internal
standards perfluorobenzene and perfluorotoluene (suggested concen-
trations of 500 ng/cartridge).
The instrumental conditions for the analysis of priority pollutants
collected on a sorbent Tenax GC sampling cartridge are given in
Table D5. The inlet manifold (Nutech Model 321) consisting of a
thermal desorption chamber and a six-port Valco valve (Valco Inst.
Corp., Houston, TX) is maintained at 270°C. The glass jet separa-
tor (or equivalent) is maintained at 250°C. The mass spectrometer
is set to scan the mass range from 25-300 daltons. The helium
purge gas through the desorption chamber is adjusted to 15 ml/min.
The nickel capillary trap on the inlet manifold is cooled with
liquid nitrogen. In a typical thermal desorption cycle, a sampling
cartridge (which has come to room temperature) is placed in the
preheated desorption chamber and the helium gas is passed through
the cartridge to purge the priority pollutant vapors into the
liquid nitrogen capillary trap [the inert activity of the trap has
been shown in previous studies (2-8)]. While the magnetic or
quadrupole instrument is continuously scanning, and after desorp-
tion has been completed, the six-port valve is rotated, the tempera-
ture on the capillary loop is rapidly raised (>150°/min), and
automatic data acquisition is initiated. The carrier gas then
introduces the vapors onto the gas chromatographic column. The
chromatographic column is held for 3 min at 60°C, programmed 8°C/
min to 160°C, and held until all compounds have eluted. After all
the components have been eluted from the gas chromatographic
column, the analytical column is then cooled to 60°C, and the next
sample is processed.
Upon completion of the chromatographic run, there are from 800-
1,400 spectra accummulated on the disk or magnetic tape which are
then subsequently processed. Depending on the information required
that day, data may then either be processed immediately, or addi-
tional samples may be run, stored on magnetic tape, and the results
examined' at a later time.
175.1 The mass spectra are processed in the following manner:
first, the original spectra are scanned, and the integrated
ion current information is extracted, then reconstructed
chromatograms are plotted (total ion intensity against the
spectrum number or elapsed time) on an electrostatic recor-
der. The information will generally indicate whether the
189
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TABLE D5. OPERATING PARAMETERS FOR GC-MS-OOMP SYSTEM (1)
Parameter
Setting
Inlet-manifold
desorption chamber and valve
capillary trap - trap cycle
inject cycle
thermal desorption time
He purge rate
GO
MS
column
He carrier flow
GC/MS interface (glass jet
separator, transfer line)
scan range
scan cycle rate, automatic cyclic
emission current
electron energy
ion energy
lens voltage
extractor voltage
samples/dalton
Available from Nutech Corp., Durham, NC.
Conditions for quadrupole instrument.
270°C
-195°C
+250°C
8 min
15 ml/min
60-160°C, 8%nin
40 ml/min
25Q°C
m/z 25+300
^2 sec
500 yA
70 eV
6 v
-100 v
8 v
1
190
-------
run is suitable for further processing since it provides
some idea of the number of unknowns in the sample and the
resolution obtained using the particular GC column condi-
tions.
175.2 For the magnetic sector instruments, the next stage of pro-
cessing generally involves the mass conversion of the spec-
tral peak times to peak masses which is done directly via
the dual disk system. A mass conversion is accomplished by
use of the calibration table obtained previously using
perfluorokerosene. Normally, one set of the calibration
data is sufficient for an entire day's data processing since
the characteristics of the Hall probe used are such that a
variation in calibration is <0.2 daltons/day. For quadru-
pole instruments, it may be necessary to check the calibra-
tion more frequently throughout the analysis period.
175.3 In many cases an estimation of the level of priority pollu-
tants by gas chromatography in combination with mass spec-
trometry is not feasible utilizing only the total ion cur-
rent. Since baseline resolution between peaks is not
always achieved, the techniques suggested are those whereby
full spectra are obtained during the chromatographic
separation step, and the selected ions are presented as
single ion plots using computer software programs. This
allows the possibility of deconvoluting constituents which
are not resolved in the total ion current chromatogram (1).
Single ion plots may be used for any combination of m/z^ ions
given in Table D6 when full spectra are obtained during"
chromatography. Thus, selectivity is increased by using a
unique ion for that particular priority pollutant, and its
intensity (peak height or area) is used for quantification.
Quantification is achieved using standards which are loaded
onto the sampling cartridges prior to instrumental analysis,
and ratioing the intensity of the priority pollutants (m/z)
to that of the perfluorobenzene and perfluorotoluene (m/z).
176 An example of the analysis of priority pollutants from an aeration
system is shown in Figures D8 and D9, and the background from a
blank Tenax GC cartridge is shown in Figure D10. The tandem chro-
matographic columns coated with Carbowax 1500 on Carbopak C and
Chromosorb W are capable of partially resolving the priority
pollutants. The final requisite resolution is achieved through
single ion profiles.
180 QUALITY ASSURANCE
181 Standard quality assurance practices should be used with this
method. Blank Tenax GC cartridges must be provided with each set
of sampling cartridges that are transported to and from the samp-
ling site. Approximately 10% of the total Tenax GC cartridges
taken to the field should be set aside as blanks. During
191
-------
TABLE D6. CHARACTERISTIC M/Z IONS SELECTED FOR
QUANTIFICATION OF PRIORITY POLLUTANTS (1)
Priority pollutant
chloromethane
dichlorodifluoromethane
bromomethane
vinyl chloride
chloroethane
dichloromethane
trichlorofluoromethane
1, 1-dichloroethylene
1, 1-dichloroethane
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloroethane
1,1, 1-trichloroethane
carbon tetrachloride
bromodi chloromethane
bis- (chloromethyl) ether
1, 2-dichloropropane
trans-1, 3-dichloropropene
tri chloroethylene
d ibromo ch loromethane
cis-1, 3-dichloropropene
1,1, 2-trichloroethane
benzene
2-chloroethylvinyl ether
bromoform
1, 1, 2, 2-tetrachloroethylene
1,1,2, 2-tetrachloroethane
toluene
chlorobenzene
M.W.
50.5
120.9
95.0
62.5
64.5
84.9
137.4
97
99
97
119.4
99
133.4
153.8
163.9
115.0
113
113
113.4
208.3
113.4
78.1
106.6
252.8
165.8
167.9
92.1
112.6
1st Ion
H/z. (D
50(100)
101(13)
94(100)
62(100)
64(100)
84(86)
101(100)
86(80)
63(100)
96(90)
83(100)
98(23)
97(100)
117(100)
127(13)
79(100)
112(4)
75(100)
130(90)
127(78)
75(100)
97(100)
78(100)
106(18)
173(100)
165(78)
168(6)
91(100)
112(100)
2nd Ion
m/z. (I)
52(33)
103(9)
86(94)
64(33)
66(33)
86(55)
103(66)
93(53)
65(33)
61(100)
85(66)
100(15)
99(66)
119(96)
129(17)
81(33)
114(3)
77(33)
132(85)
208(13)
77(33)
99(63)
79(6)
63(95)
175(50)
166(100)
137(7)
92(78)
114(33)
3rd Ion
m/z_ (I)
-
87(33)
-
-
-
49(100)
-
61(100)
83(13)
98(57)
-
62(100)
-
121(30)
85(66)
-
65(33)
-
97(66)
206(10)
-
132(9)
-
-
252(11)
129(64)
133(7)
-
-
(continued)
192
-------
TABLE D6 (cont'd.)
Priority pollutant
ethylbenzene
acrolein
acrylonitrile
perf luorobenzene
perfluoro toluene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
M.W.
106.2
56.1
53
186
235
1st Ion
m/z (I)
106(33)
56(83)
53(99)
186(100)
186(100)
146(100)
146(100)
2nd Ion
m/z. (I)
91(100)
55(65)
52(75)
-
263(100)
150(10)
150(11)
3rd Ion
m/z (I)
-
-
51(32)
117(13)
-
-
193
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196
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instrumental analysis a blank is analyzed first and then one is
analyzed after every tenth sample. Likewise a control cartridge
which contains known quantities of priority pollutants and has
been transported to and from the sampling site as well as stored
under the same conditions as the samples is to be analyzed after
each blank. In this manner, RMR factors are generated from 10% of
all the samples which are analyzed and provide the ability to cal-
culate an average RMR value for each priority pollutant throughout
the sample analysis period.
182 Field replicates (three) should be collected to validate the preci-
sion of the sampling technique. Laboratory replicates should be
analyzed to validate the precision of the analysis and for deter-
mining the relative molar response factors (RMR). Where doubt
exists over the identification of a peak from single ion plots,
confirmation should be accomplished by comparing the observed ion
intensity ratios of the priority pollutants in the collected sample
with those observed for the authentic compound and/qr the compari-
son of both mass spectra.
183 A sampling protocol such as that shown in Figure Dll should bemused
to document the history and provide the necessary information con-
cerning each Tenax GC cartridge used. Sampling protocols are to
be filled out in duplicate so that a backup record is available in
the event of the loss of the original protocol. A sample code is
generated as shown on the sampling protocol (Fig. Dll) which is
placed on the sample container of the Tenax GC cartridge and it and
the chain of custody form (Table D7) are concurrently transferred
with the sample from one analyst to the next throughout the col-
lection and analysis procedure.
190 CALCULATIONS AND REPORTING
191 In order to eliminate the need to obtain complete calibration cur-
ves for each priority pollutant for which quantitative information
is desired, the method of relative molar response (RMR) factors is
used (7,8). Successful use of this method requires information on
the exact amount of standard added and the relationship of RMR
(unknown) to the RMR (standards). The method of calculation is as
follows:
A , /Moles ,
,.. v _ unk unk
unknown/standard A ,/Moles ,
std std
A = peak area, determined by integration or triangulation.
The value of RMR is determined from at least three independent analyses.
197
-------
I
Date:
Project No. (/
Operator Qf £)
Trip No. L
Sampler O/ a)
Area SJ^.fiL i
Address ~]i LJ^.
Period ("£r
Site
location- ( £.
Sample Code
WO
(tffi)
fC?37 -
H5I
J21 (TO)
DC *»?« ^3. 5
t*tt O.t)5 (lp«)
3 ("»»)
Ead:
SUrt:
Toul:
3 \\.to
3. I
DuPent (OP)
S*«pliai rat* (iait.)
Sa«pliaf r«tt (final)
End: Tla«
Start: Ti««
Toul: (•!&)
MSA (MSA)
(ip«) Suplim r»t« (init.) Wp«)
(1pm) SupliBf rat* (fioal) (*;•)
End: Tiae Count ______
Start: Tiaw ____ Count ______
Total: (Bin) ___ Count ______
•I/count ^^^^^^^^^^
Remarks
Voluae Air/Cartridge 9
MAP:
Time Temp. Wet. Dry
Rel. Humid % Wind Dir./Speed _/_
Cloud Odor
Remarks
Time Temp. Wet. Dry
Rel. Humid % Wind Dir./Speed /_
Cloud Odor ____________
Remarks
Time Temp. Wet. Dry
Rel. Humid t. Wind Dir./Speed
Cloud Odor
Remarks
Time Temp. Wet Dry
Rel. Humid % Wind Dir./Speed __/_
Cloud Odor
Remarks
Figure Dll. Field Sampling Protocol Sheet - A
198
-------
TABLE D7. CHAIN OF CUSTODY RECORD
Research Triangle Institute
Analytical Sciences Division
Chemistry and Life Sciences Group
Research Triangle Park, NC 27709
SAMPLE CODE:
Sample Type : Cu
No. of Containers:
Volume Collected:
1JL/ <-«J.
Volume Analyzed:
1JL
Relinguished
By:
Operation Performed (aliquot, std. cone.,
remarks, etc.)
199
-------
A . /g ,/GMW ,
unk &unk unk
A = peak' area, as above
g = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
(3) g.
'unk
A T -GMW , *g . ,
unk unk std
A .,«GMW _j
std std
. , „,
unk/ std
Examples are given in Table D8.
192 The standards may be added as internal standards prior to samp-
ling; however, since the volume of air taken for each sample is
accurately known, it is also possible and more practical to use the
external standard technique whereby the standard is introduced into
the cartridge after sampling but prior to analysis. Previously,
it has been determined that the retention times for these two com-
pounds are such that they elute at approximately midpoint in the
chroma tographic run, and their retention time, as well as mass
spectra, do not interfere with the analysis of the priority pollu-
tants .
193 Since the volume of purge air taken to produce a given sample is
accurately known, and an external stadnard is added to the sample,
then the weight can be determined per cartridge, and hence, the
concentration of the unknown per unit volume. The approach for
quantifying the priority pollutants requires that the RMR is deter-
mined for each constituent of interest. This means that when a
sample has been taken, the external standard must be added at a
known concentration.
194 Results of analysis are expressed as ng/min/ft2 pond surface for
samples taken from open aeration systems and as ng/m3for samples
from closed chambers since the recovery of priority pollutants from
raw wastewater or activated sludge is highly variable (1) .
REFERENCES
1. E. D. Pellizzari. "Development of Method for Collection and Analysis of
Consent Decree Purgeable Organics Emitted From Municipal Treatment
Plants", EPA Contract No. 68-03-2681, October, 1978, 162 pp.
2. E. D. Pellizzari. "Development of Method for Carcinogenic Vapor Analy-
sis in Ambient Atmospheres", EPA-650/ 2- 74-121, July, 1974, 148 pp.
200
-------
TABLE D8. EXAMPLES OF PREVIOUSLY DETERMINED RELATIVE MOLAR RESPONSE
FACTORS FOR SEVERAL PRIORITY POLLUTANTS USING SELECTIVE M/Z IONS
Priority pollutant
methyl bromide
dichloromethane
1, 1-dichloroethylene
acrylonitrile
1, 2-trans-dichloroethylene
chloroform
1, 2-dichloro ethane
1, 1, 1-trichloroethane
carbon tetrachloride
bromodichloromethane
1, 2-dichloropropane
benzene
trichloroethylene
bromoform
tetrachloroethylene
toluene
ethylbenzene
chlorobenzene
1, 2-dichlorobenzene
1, 3-dichlorobenzene
m/jz
94
84
96
53
61
83
98
97
117
127
112
78
130
171
170
93
106
112
150
150
ii-PFB
(m/_z-186)
0.104 + 0.008a
0.134 + 0.002
0.341 + 0.049
0.037 + 0.005
0.098 + 0.016
0.093 + 0.013
0.016 + 0.005
0.119 + 0.004
0.075 + 0.005
0.017 + 0.004
0.004 + 0
0.024 + 0.032
0.071 + 0.017
0.036 + 0.007
0.019 + 0.003
0.019 + 0.002.
0.254 + 0.047
0.341 + 0.048
0.039 + 0.002
0.015 + 0.001
iS-PFT
(m/^-236)
0.076 + 0.002
0.104 + 0.007
0.249 + 0.041
0.027 + 0.003
0.070 + 0.007
0.071 + 0.016
0.011 + 0.001
0.095 + 0.013
0.054 + 0.004
0.013 + 0.003
0.032 +0.004
0.187 + 0.038
0.052 + 0.013
0.026 + 0.004
0.013 + 0.002
0.014 + 0.002
0.184 + 0.036
0.248 +0.039
0.0295 + 0
0.0115 + 0
Average of triplicate determinations,
201
-------
3. E. D. Pellizzari. "Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors", EPA-600/2-75-076, November,
1975, 186 pp.
4. E. D. Pellizzari. "The Measurement of Carcinogenic Vapors in Ambient
Atmospheres", EPA-600/7-77-055, June, 1977, 288 pp.
5. E. D. Pellizzari. "Measurement of Carcinogenic Vapors in Ambient Atmos-
pheres", EPA-600/7-78-062, April, 1978, 237 pp.
6. E. D. Pellizzari. "Improvement of Methodologies for the Collection and
Analysis of Carcinogenic Vapors", EPA Contract No. 68-02-7264, in
preparation.
7. E. D. Pellizzari. "Identification and Analysis of Ambient Air Pollu-
tants Using the Combined Techniques of Gas Chromatography and Mass
Spectrometry", EPA Contract No. 68-02-2262, .in preparation.
8. E. D. Pellizzari. "Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy", EPA-600/2-77-100, June, 1977, 104 pp.
202
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/2-80-017
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
COLLECTION AND ANALYSIS OF PURGEABLE ORGANICS
EMITTED FROM WASTEWATER TREATMENT PLANTS
5. REPORT DATE
March 1980 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Edo D. Pellizzari and Linda Little
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
1BC611, SOS#5, BE 23B
27709
11. CONTRACT/GRANT NO.
68-03-2681
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory—Cin.,OH
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final June 1978-Marnh 1979
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officers: Howard 0. Wall (513) 684-7659 and Dolloff F. Bishop (513) 684-7628
16. ABSTRACT
An analytical method was developed for the analysis of volatile priority pollu-
tants in airstreams passing through wastewaters using a Tenax GC cartridge in com-
bination with gas chromatography/mass spectrometry/computer, A sampling system was
designed and field tested for sampling airstreams passing through grit chambers and
activated sludge systems. Recovery of the volatile priority pollutants was accom-
plished by thermal desorption, purging with helium into a liquid-nitrogen-cooled
nickel capillary trap, and releasing the vapors onto a gas chromatog'raphic column.
Characterization and quantification of the priority pollutants was accomplished by
GC-mass spectrometry. The areas of investigation included: (a) the performance
of a Tenax GC sampling cartridge for the priority pollutants in the airstreams
passing through wastewaters; (b) the design, fabrication and evaluation of a field
sampler; (c) recovery studies of priority pollutants from distilled water, raw
wastewaters and activated sludge using laboratory-simulated conditions; (d) a
methods-of-addition study for priority pollutants in raw wastewaters and activated
sludge; (e) the delineation of the GC/MS/COMP operating parameters for priority
pollutants collected on Tenax GC cartridges; (f) the application of the developed
methods to the-analysis of priority pollutants in airstreams passing through raw
wastewaters and activated sludge, and (g) evaluation of the accuracy and precision
of the collection methods.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Organic compounds
Wastewater
Activated sludge
Collection
Airstreams
Chemical analysis
Sampling
Mass spectroscopy
Gas chromatography
Purgeable organics
Priority pollutants
07C
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
215
2O. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
203
U.S. GOVERNMENT PRINTING OFFICE: 1980 -657-146/5699
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