600282056
VOLATILE ORGANICS IN AERATION GASES AT
MUNICIPAL TREATMENT PLANTS
by
Edo D. Pellizzari
Analytical Sciences Division
Chemistry and Life Sciences Group
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-03-2780
Project Officers
James J. Westrick and Paul Warner
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 publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U. S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
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ABSTRACT
Utilizing previously developed and validated analytical methods, research
was conducted to: (1) estimate volatile (purgeable) Priority Pollutants
stripped from aeration basins at a Municipal Wastewater Treatment Facility;
(2) determine the volatile Priority Pollutants in wastewater and activated
sludge of a treatment facility; (3) determine the equilibrium distribution
of volatile Priority Pollutants between the solid and aqueous phases for
wastewater and activated sludge; (4) measure volatile pollutants produced by
stabilization of sludge by superchlorination; and (5) determine, if any, the
chlorinated organics produced during superchlorination of sludge. Liquid
and gas sampling strategies were developed to obtain representative data on
the emission of purgeable Priority Pollutants from aeration basins of a
municipal wastewater treatment facility.
This report was submitted in fulfillment of Contract No. 68-03-2780
by the Research Triangle Institute under the sponsorship of the U. S. Environ-
mental Protection Agency.
111
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iv
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CONTENTS
Abstract iii
Figures vi
Tables xvi
Acknowledgment xix
1. Introduction 1
2. Conclusions 3
3. Recommendations 6
4. Program Objectives 7
5. Partitioning of "Purgeable" Priority Pollutants Between
Aqueous and Solid Phases in Activated Sludge Samples . . 8
6. Estimation of Purgeable Priority Pollutant Levels in Air-
streams from Activated Sludge 29
7. Identification of Chlorinated Compounds in Sludge From a
Superchlorination Process 53
References 84
Appendices
A. GC/MS/COMP Profiles of Fractions Obtained for Samples from
Fayetteville, NC Superchlorination Process 85
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FIGURES
No.. Page
1 Potential gas-liquid-solid equilibria in aeration basin 8
2 Flow diagram of Northside Treatment Sewage Plant, Durham, NC . . . . 11
3 Schematic of sampler system for grit chambers and aeration tanks . . 30
4 Schematic of sampling shroud 32
5 Diagram of pneumatics in sampling system 33
6 Schematic of Superchlorination process at Rocky Mount and
Fayetteville, NC and locations of sampling 54
7 Sampling locations for settling beds at the Rocky Mount, NC site . . 55
8 Chlorinated sludge entering settling bed at Fayetteville Municipal
Wastewater Treatment Facility 56
Al Electron impact GC/MS/COMP profile of solvent blank (SP2100, 0.23
mm i.d. x 25 m fused silica capillary) 86
A2 Negative chemical ionization GC/MS/COMP profile of solvent blank
(SP2100, 0.23 mm i.d. x 25 m fused silica blank) 87
A3 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of solvent blank (SP2100, 0.23 mm i.d. x 25 m
fused silica capillary) 88
A4 Electron impact GC/MS/COMP profile of "Neutral" fraction for
Influent No. 2 to superchlorination process (SP2100 Hewlett-
Packard fused silica capillary - 0.23 mm i.d. x 25 m) 89
A5 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion of Influent No. 2 to superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica capillary) 90
A6 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "neutral" fraction of Influent No. 2 to
superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused
silica capillary) 91
VI
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FIGURES CONT'D.
No. Page
A7 Electron impact GC/MS/COMP profile for "neutral" fraction for
Influent No. 3 from superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica capillary) 92
A8 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Influent No. 3 from superchlorination process (SP2100
0.23 mm i.d. x 25 m fused silica capillary) 93
A9 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "neutral" fraction for Influent No. 3
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m
fused silica capillary 94
A10 Electron impact GC/MS/COMP profile of "neutral" fraction for
Effluent No. 1 from superchlorination process (SP2100, 0.23 mm
i.d. x 25 m fused silica capillary) 95
All Negative chemical ionization GC/MS/COMP profile of "neutral" fraction
for Effluent No. 1 from superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica) 96
A12 Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35,
37, 79, 81) of "neutral" fraction for Effluent No. 2 from
superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused
silica capillary) 97
A13 Electron impact GC/MS/COMP profile of "neutral" fraction for
Effluent No. 2 from superchlorination process (SP2100, 0.23 mm
i.d. x 25 m fused silica capillary) 98
A14 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Effluent No. 2 superchlorination process (SP2100,
0.23 mm i.d. x 25 m, fused silica capillary) 99
A15 Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35,
37, 79, 81) of "neutral" fraction for Effluent No. 2 from
superchlorination process (SP2100, 0.23 mm x 25 m fused
silica capillary) 100
vzi
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FIGURES CONT'D.
No. Page
A16 Electron impact GC/MS/COMP profile of "neutral" fraction for
Effluent No. 3 from superchlorination process (SP2100, 0.23 mm
i.d. x 25 m, fused silica capillary) 101
A17 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Effluent No. 3 superchlorination process (SP2100,
0.23 mm i.d. x 25 m, fused silica capillary) 102
A18 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "neutral" fraction for Effluent No. 3 from
superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused
silica capillary) 103
A19 Electron impact GC/MS/COMP profile of "neutral" fraction for
Settling Bed Sample from superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica capillary) 104
A20 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Settling Bed Sample superchlorination process
(SP2100, 0.23 mm i.d. x 25 m fused silica capillary) 105
A21 Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35,
37, 79, 81) of "neutral" fraction for Settling Bed Sample
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m,
fused silica capillary) 106
A22 Electron impact GC/MS/COMP profile of "acid" fraction for Influent
No. 1 from superchlorination process (SP1240 DA packed column) 107
A23 Negative chemical ionization GC/MS/COMP profile of "acid" fraction
for Influent No. 1 from superchlorination process (SP1240
DA packed column) 108
A24 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "acid" fraction for Influent No. 1 from
superchlorination process (SP1240 DA packed column) 109
A25 Electron impact GC/MS/COMP profile of "acid" fraction for Influent
No. 2 from superchlorination process (SP1240 DA packed column) 110
Vlll
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FIGURES CONT'D.
No. Page
A26 Negative chemical ionization GC/MS/COMP profile of "acid" fraction
from Influent No. 2 for superchlorination process (SP1240 DA
packed column) Ill
A27 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "acid" fraction for Influent No. 2 from
superchlorination process (SP1240 DA packed column) 112
A28 Electron impact GC/MS/COMP profile of "acid" fraction for Influent
No. 3 from superchlorination process (SP1240 DA packed column) 113
A29 Negative chemical ionization GC/MS/COMP profile of "acid" fraction
for Influent No. 3 from superchlorination process (SP1240 DA
packed column) 114
A30 Negative chemical ionization GC/MS/COMP single ion profiles of
"acid" fraction for Influent No. 3 for superchlorination
process (SP1240 DA packed column) 115
A31 Electron impact GC/MS/COMP profile of "acid" fraction for Effluent
No. 1 from superchlorination process (SP1240 DA packed column) 116
A32 Negative chemical ionization GC/MS/COMP profile of "acid" fraction
for Effluent No. 1 from superchlorination process (SP1240 DA
packed column) 117
A33 Negative chemical ionization GC/MS/COMP single ion profiles (m/z^
35, 37, 79, 81) of "acid" fraction for Effluent No. 1 from
superchlorination process (SP1240 DA packed column) 118
A34 Electron impact GC/MS/COMP profile of "acid" fraction for Effluent
No. 2 from superchlorination process (SP1240 DA packed column) 119
A35 Negative chemical ionization GC/MS/COMP profile of "acid" frac-
tion for Effluent No. 2 from superchlorination process (SP1240
DA packed column) 120
A36 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "acid" fraction for Effluent No. 2 from
superchlorination process (SP1240 DA packed column) 121
A37 Electron impact GC/MS/COMP profile of "acid" fraction for Effluent
No. 3 from superchlorination process (SP1240 DA packed column) 122
IX
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FIGURES CONT'D.
No. Page
A38 Negative chemical ionization GC/MS/COMP profile of "acid" frac-
tion from Effluent No. 3 from superchlorination process
(SP1240 DA packed column) 123
A39 Negative chemical ionization GC/MS/COMP single ion profiles (m/:z
35, 37, 79, 81) of "acid" fraction for Effluent No. 3 from
superchlorination process (SP1240 DA packed column) 124
A40 Electron impact GC/MS/COMP profile of "acid" fraction for Settling
Bed Sample from superchlorination process (SP1240 DA packed
column) 125
A41 Negative chemical ionization GC/MS/COMP profile of "acid" fraction
from Settling Bed Sample for superchlorination process (SP1240
DA packed column) 126
A42 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "acid" fraction for Settling Bed Sample
from superchlorination process (SP1240 DA packed column) . . . 127
A43 Electron impact GC/MS/COMP profile of "acid" solvent blank (SP1240
DA packed column) 128
A44 Negative chemical ionization GC/MS/COMP profile of "acid" solvent
blank (SP2100 packed column) 129
A45 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "acid" solvent blank (SP1240 DA packed
column) 130
A46 Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for
Influent No. 2 (SP2100 capillary) 131
A47 Negative chemical ionization GC/MS/COMP profile of GP1 "neutral"
fraction for Influent No. 2 (SP2100 capillary) 132
A48 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GP1 "neutral" fraction for Influent No. 2
(SP2100 capillary) . 133
A49 Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Influent No. 2 sample (SP2100 capillary) 134
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FIGURES CONT'D.
No. Page
A50 Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
fraction of Influent No. 2 sample (SP2100 capillary) 135
A51 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GP4 "neutral" fraction for Influent No. 2
sample (SP2100 capillary) 136
A52 Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Influent No. 3 sample (SP2100 capillary) 137
A53 Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
fraction for Influent No. 3 (SP2100 capillary) 138
A54 Negative chemical ionization GC/MS/COMP single ion profiles of "neu-
tral" fraction for Influent No. 3 sample (SP2100 capillary). . 139
A55 Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for
Effluent No. 2 sample (SP2100 capillary) 140
A56 Negative chemical ionization GC/MS/COMP profile of GP1 "neutral"
fraction for Effluent No. 2 sample (SP2100 capillary) 141
A57 Negative chemical ionization GC/MS/COMP single ion profiles of GP1
"neutral" fraction for Effluent No. 2 sample (SP2100 capillary) 142
A58 Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Effluent No. 2 (SP2100 capillary) 143
A59 Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
fraction of Effluent No. 2 (SP2100 capillary) 144
A60 Negative chemical ionization GC/MS/COMP single ion profiles (m/£
35, 37, 79, 81) of GP4 "neutral" fraction of Effluent No. 2
(SP2100 capillary) 145
A61 Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for
Effluent No. 3 (SP2100 capillary) 146
A62 Negative chemical ionization GC/MS/COMP profile of GP1 "neutral"
fraction of Effluent No. 3 (SP2100 capillary) 147
A63 Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35,
37, 79, 81) of GP1 "neutral" fraction for Effluent No. 3
(SP2100 capillary) 148
XI
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FIGURES CONT'D.
No. Page
A64 Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Effluent No. 3 sample (SP2100 capillary) 149
A65 Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
fraction for Effluent No. 3 (SP2100 capillary) 150
A66 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GP4 "neutral" fraction for Effluent No. 3
(SP2100 capillary) 151
A67 Electron impact GC/MS/COMP profile of GP1 "neutral" solvent blank
(SP2100 capillary) 152
A68 Negative chemical ionization GC/MS/COMP profile of GP1 "neutral"
solvent blank (SP2100 capillary) 153
A69 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GP1 "neutral" solvent blank (SP2100
capillary) 154
A70 Electron impact GC/MS/COMP profile of GP4 "neutral" solvent blank
(SP2100 capillary) 155
A71 Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
solvent blank (SP2100 capillary) 156
A72 Negative chemical ionization GC/MS/COMP single ion profiles of GP4
"neutral" solvent blank (SP2100 capillary) 157
A73 Negative chemical ionization GC/MS/COMP profile of GPA 1 "acid"
fraction for Influent No. 1 sample from superchlorination
process 158
A74 Negative chemical ionization GC/MS/COMP single ion profiles (m/^z
35, 37, 79, 81) of GPA 1 "acid" fraction for Influent No. 1
sample from superchlorination process 159
A75 Electron impact GC/MS/COMP profile of GPA 1 fraction for Influent
No. 2 from superchlorination process 160
A76 Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction
for Influent No. 2 from superchlorination process 161
XII
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FIGURES CONT'D.
No. Page
A77 Negative chemical ionization GC/MS/COMP single ion profiles (m/jz
35, 37, 79, 81) of GPA 1 fraction for Influent No. 2 from
superchlorination process 162
A78 Electron impact GC/MS/COMP profile of GPA 1 fraction for Influent
No. 3 from superchlorination process 163
A79 Electron impact GC/MS/COMP profile of GPA 1 for Effluent No. 2
from superchlorination process 164
A80 Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction
for Effluent No. 2 from superchlorination process 165
A81 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GPA 1 fraction for Effluent No. 2 from
superchlorination process 166
A82 Electron impact GC/MS/COMP profile of GPA 1 fraction from Effluent
No. 3 for superchlorination process 167
A83 Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction
for Effluent No. 3 from superchlorination process 168
A84 Negative chemical ionization GC/MS/COMP single ion profiles (m/z^
35, 37, 79, 81) for Effluent No. 3 from superchlorination
process 169
A85 Electron impact GC/MS/COMP profile of GPA 1 "blank" 170
A86 Negative chemical ionization GC/MS/COMP profile of GPA 1 for "blank" 171
A87 Negative chemical ionization GC/MS/COMP profiles (m/z 35, 37, 79,
81) of GPA 1 for "blank" 172
A88 Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent
No. 2 from superchlorination process 173
A89 Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction
for Influent No. 2 from superchlorination process 174
A90 Negative chemical ionization GC/MS/COMP single ion profiles (m/z^
35, 37, 79, 81) of GPA 4 fraction for Influent No. 2 from
superchlorination process 175
A91 Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction
for Effluent No. 2 from superchlorination process 176
Xlll
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FIGURES CONT'D.
Page
A92 Electron impact GC/MS/COMP profile of GPA 4 for Effluent No. 2
from superchlorination process ................ 177
A93 Negative chemical ionization GC/MS/COMP single ion profiles of
GPA 4 fraction for Effluent No. 2 from superchlorination pro-
cess ............................. 178
A94 Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent
No. 3 from superchlorination process ............. 179
A95 Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent
No. 3 from superchlorination process ............. 180
A96 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GPA 4 fraction for Influent No. 3 from
superchlorination process ................... 181
A97 Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction
for Effluent No. 3 from superchlorination process ....... 182
A98 Negative chemical ionization GC/MS/COMP profile single ion profiles
(m/z 35, 37, 79, 81) of GPA 4 fraction for Effluent No. 3
from superchlorination process ................ 183
A99 Negative chemical ionization GC/MS/COMP profile of GPA 4 "blank". . 184
A100 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of GPA 4 "blank" ............... 185
A101 Electron impact GC/MS/COMP profile of Si-neutral THF fraction for
Effluent No. 1 (SP2100 capillary) ............... 186
A102 Negative chemical ionization GC/MS/COMP profile of Sl-THF fraction
for Effluent No. 1 (SP2100 capillary) ............. 187
A103 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of Sl-THF fraction for Effluent No. 1
(SP2100 capillary) ...................... 188
A104 Electron impact GC/MS/COMP profile of S3-neutral acetone fraction
of Effluent No. 1 (SP2100 capillary) ............. 189
A105 Negative chemical ionization GC/MS/COMP profile of S3-neutral ace-
tone fraction for Effluent No. 1 (SP2100 capillary) ...... 190
xiv
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FIGURES CONT'D.
No. Page
A106 Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35,
37, 79, 81) of S3-neutral acetone fraction for Effluent No. 1
(SP2100 capillary) 191
A107 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Effluent No. 2 from superchlorination process (Cl.
unquenched in sample) 192
A108 Negative chemical ionization GC/MS/COMP profile of "neutral" frac-
tion for Effluent No. 2 from superchlorination process (C12
quenched in sample) 193
A109 Negative chemical ionization GC/MS/COMP for ion profiles (m/z 35, 37,
79, 81) of "neutral" fraction for Effluent No. 2 from super-
chlorination process (Cl_ quenched in sample) 194
A110 Negative chemical ionization GC/MS/COMP single ion profiles (m/z
35, 37, 79, 81) of "neutral" fraction for Effluent No. 2 from
superchlorination process (C10 in sample unquenched) 195
xv
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TABLES
No. Page
—^^^— — -- *i?
1 Sampling Parameters for Activated Sludge: Pilot Study - Northside
Treatment Plant, Durham, NC 12
2 Sampling Parameters for Activated Sludge: Pilot Study No. 2 -
Northside Treatment Plant, Durham, NC 13
3 Adsorption of Chlorobenzene and Bromobenzene to Activated Sludge. . 15
4 Adsorption of Chlorobenzene and Bromobenzene to Activated Sludge. . 15
5 Effect of Spiking Carrier Volume on Freundlich Adsorption Isotherm
Parameters for Benzene in Activated Sludge 17
6 Freundlich Adsorption Isotherm Parameters: Selected Priority
Pollutants in Activated Sludge - Pilot Study at Northside
Treatment Plant, Durham, NC 19
7 Freundlich Adsorption Isotherm Parameters for Selected Priority
Pollutants in Activated Sludge: Northside Treatment Plant,
Durham, NC - Experiment No. 1 21
8 Variation of Freundlich Adsorption Isotherm Parameters for
Selected Priority Pollutants in Activated Sludge 26
9 Variation of Freundlich Adsorption Isotherm Parameters for
Selected Priority Pollutants in Activated Sludge - Mean + S.D.
(C.V.) for all Data in Table 7 27
10 Comparison of Freundlich Adsorption Isotherm Parameters for
Selected Priority Pollutants in Raw Wastewater Influent with
Activated Sludge: Northside Treatment Plant, Durham, NC -
Experiment No. 2 28
11 Sampling Protocol for Air and Sludge Samples: Pilot Study -
Northside Treatment Plant, Durham, NC 35
12 Sampling Protocols for Air, Activated Sludge and Raw Wastewater
Samples: Experiments 1 & 2 - Northside Treatment Plant,
Durham, NC 36
xvi
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TABLES CONT'D.
No. Page
13 Recovery of Priority Pollutants Used in Quality Control 39
14 Priority Pollutants Levels in Airstreams and Activated Sludge
from Aeration Tank No. 2: Pilot Study - Northside Treatment
Plant, Durham, NC. 40
15 Comparison of Priority Pollutant Levels in Activated Sludge at
Two Different Time Periods: Northside Treatment Plant,
Durham, NC - Pilot Study 42
16 Priority Pollutant Levels in Raw Wastewater: Northside Treatment
Plant, Durham, NC - Experiment No. 1 43
17 Priority Pollutant Levels in Airstreams and Activated Sludge from
Aeration Tank No. 2: Northside Treatment Plant, Durham, NC -
Experiment No. 1 45
18 Priority Pollutant Levels in Airstreams and Activated Sludge from
Aeration Tank No. 4: Northside Treatment Plant, Durham, NC -
Experiment No. 2 48
19 Estimated Emission Rates Calculated for Selected Priority Pollutants
from Aeration Basins at Northside Treatment Plant, Durham, NC. 52
20 Sampling Protocol for Superchlorination Process at Wastewater
Treatment Plant in Rocky Mount, NC 58
21 Sampling Protocol for Superchlorination Process at Wastewater
Treatment Facility in Fayetteville, NC 59
22 GC/MS Conditions for Fayetteville Acid Fractions 65
23 GC/MS Conditions for Other Fayetteville Fractions 66
24 Organic Chlorine Content for Fayetteville, NC Superchlorinated
Sludges 68
25 "Purgeable" Chlorinated Compounds Identified in Effluent from a
Superchlorination at Rocky Mount, NC Facility 69
26 Chlorinated Compounds Identified in the Neutral Fraction of
Effluent from the Superchlorination at Rocky Mount, NC
Facility 70
27 Chlorinated Compounds Identified in the Acid Fraction of Effluent
from the Superchlorination at Rocky Mount Facility 71
xvi i
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TABLES CONT'D.
No.
28 Chlorinated Compounds Identified in the Neutral Fraction of Sludge
from Settling Bed of the Superchlorination at Rocky Mount, NC
Facility 72
29 Chlorinated Compounds Identified in the Acid Fraction of Sludge
from Settling Bed of the Superchlorination Process at Rocky
Mount, NC Facility 73
30 Levels of Selected "Purgeable" Organics in Liquid Sludge Before and
After Superchlorination at the Rocky Mount, NC Facility. ... 75
31 Extracts and Fractions Produced During Sample Processing for
Extractables (Fayetteville, NC) 77
32 Comparison of Chlorinated Cyclohexanes in Chlorine Quenched and
Unquenched Superchlorination Process Samples 81
33 Chlorinated Compounds Identified in Fayetteville, NC - Neutral
Fractions 82
34 Chlorinated Compounds Identified in Fayetteville, NC Acid Fractions 83
XVlll
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ACKNOWLEDGEMENTS
The author wishes to thank the personnel at the Rocky Mount, Fayetteville
and Northside Durham Municipal Treatment Facilities for their assistance and
cooperation during the course of the study. The valuable assistance of
Messrs. J. Davis, M. Hunicutt, J. Bunch, and J. Chen, and Ms. D. Smith for
executing laboratory and field experiments is gratefully appreciated.
The constant encouragement and helpful criticism of Messrs. J. Westrick,
D. F. Bishop, J. Cohen, and P. Warner of the Municipal Environmental Research
Laboratory, Environmental Protection Agency, Cincinnati, OH are deeply
appreciated.
xix
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SECTION 1
INTRODUCTION
Until this program was initiated a paucity of data was available on the
composition and levels of volatile organics in off-gas from aeration basins
of wastewater treatment facilities. In fact, a method did not exist for the
sampling and analysis of volatile organics in the off-gases until EPA sponso-
red a program for its development (Contract No. 68-03-2681). The need to
know the Priority Pollutant burden in the gases emitted from grit chambers
and aeration basins is important since it could have an impact on air quality
near wastewater treatment facilities. This research program addressed the
question of how the levels of Priority Pollutants which are released into
the ambient air can be measured. Essentially there are two ways that can be
employed to measure the emissions of Priority Pollutants due to air stripping
in grit chambers and aeration basins for activated sludge. The first utilizes
the direct sampling of the off-gas and quantifying the volatile organic
components collected in these samples. The second utilizes an indirect
measurement method in that the volatile organic compounds are measured in
the liquid and by using the Henry's Law relationship, an estimation of the
vaporization of the compounds of interest is made. In order to utilize the
Henry's Law relationship, it is necessary to know the mass transfer coeffi-
cient. In activated sludge basins the potential sorption of volatile organics
to solids may affect the mass transfer coefficient and thus complicate the
use of a simple Henry's Law relationship. Information which provides an
insight to the measurement of emissions as a result of off-gassing from
aeration basins has been obtained in this research program. The effect of
sorption of volatile organics to the solids in activated sludge was also
examined.
Because the sludge cake generated from superchlorination of sludge can
eventually be delivered to a landfill or used as fertilizer, it is also
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important to know whether potentially toxic materials are generated by this
process. Little information is available on the chemical characterization
of chlorinated sludge, and since the process is in operation at some waste-
water treatment facilities a characterization study was conducted.
This report describes the results obtained in these two major areas of
investigation.
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SECTION 2
CONCLUSIONS
14
C-Radiolabeled chlorobenzene, toluene, benzene, chloroform, trichloro-
ethylene, carbon tetrachloride and bromobenzene were used to determine the
extent of sorption by the solids in activated sludge and raw wastewater.
The Freundlich Adsorption Isotherm relationship was used to describe the
sorption capacity and intensity of the solid for each of the radiolabeled
compounds. Measurable sorption capacities (K) were detected for each of the
Priority Pollutants. Sorption studies conducted over several different time
periods indicated large variations in K values, e.g., for chloroform it
ranged from 0.62 to 3.54. The sorption intensity (n) for several chemicals
varied by as much as a factor of 3. The results indicated that the sorption
of volatile chemicals to the solid phase in activated sludge cannot be
ignored when attempting to predict their concentration in the off-gas by
using liquid phase concentrations. The sorption capacity for the same
chemicals to solids in raw wastewater was deemed negligible.
A pilot study and two experiments were conducted on different days to
determine the levels of volatile Priority Pollutants in the off-gas from
aeration basins and in activated sludge and raw wastewater at the Northside
Treatment plant in Durham, NC. Methylene chlorine, 1,1-dichloroethane,
trans-1,2-dichloroethylene, chloroform, 1,2-dichloroethane, carbon tetra-
chloride, bromodichloromethane, trichloroethylene, benzene, tetrachloroethy-
lene, toluene, o-dichlorobenzene, and m-dichlorobenzene were detected in the
off-gas. In general, the concentrations of Priority Pollutants were higher
at the front end of the aeration basin than either the middle or end of the
basin. In general, a decrease by a factor of 2 to 3 was observed. In
contrast the levels of Priority Pollutants measured in the activated sludge
did not appear to decrease at the same three points across the aeration
basin. The concentrations of Priority Pollutants in raw wastewater were
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higher, however, than in the activated sludge itself indicating that the
Priority Pollutants were partially lost at other points in the treatment
facility or that a dilution had occurred prior to reaching the aeration
basin. Since significant sorption for the Priority Pollutants to the solid
in activated sludge and the lack of a concentration gradient across an
aeration basin was observed, it was concluded that the use of liquid phase
concentrations to predict the off-gas concentrations for the same Priority
Pollutants cannot be accomplished accurately using a simple Henry's Law
relationship.
The emission rate from the entire composite aeration tank area for the
Northside Treatment Plant in Durham, NC was determined for a number of
Priority Pollutants. Four Priority Pollutants exhibited emission rates >1
kg/h. The highest rates were observed for chloroform and tetrachloroethylene
with emission reaching 5.7 kg/h and 7.0 kg/h, respectively.
Sampling and analysis for chlorinated compounds in superchlorinated
sludge revealed the presence of several hundred chlorinated constituents.
The measurement of organic chlorine in the solid phase from the effluent of
superchlorinated sludge indicated the presence of 2 to 4 1/2% organic chlorine.
The organic chlorine content for the influent was not detectable using the
Schoniger method. The application of negative ion chemical ionization/mass
spectrometry (NICI/MS) greatly facilitated the specific and sensitive detec-
tion of chlorinated compounds. Quantification of purgeable Priority Pollu-
tants prior to and after chlorination of sludge indicated increases in their
concentrations. Chloroform increased from ~6 ppb to over 1,000 ppb before
and after chlorination of sludge, while carbon tetrachloride was not detected
in the influent and was measured at levels upto 989 ppb in the chlorinated
sludge effluent. Increases of almost three orders of magnitude were also
observed for £-chlorotoluene, in some cases from only trace levels to 1,620
ppb. Likewise analysis of acid, base and neutral fractions utilizing the
Priority Pollutant method for sludge analysis yielded only a few chlorinated
nonpriority pollutants in these fractions. In contrast the examination of
the "discard" fraction generated by this method by NICI/MS indicated that
the majority of the chlorinated compounds were contained in these fractions
which were amenable to gas chromatography. Even though quantification of
-------
the chlorinated compounds detected by NICI/MS was not conducted, it was
evident that a major portion of the chlorinated organics was not detected by
this method since the Schb'niger method had demonstrated the presence of up
to 4-1/2% organic chlorine in the solid component of the chlorinated sludge.
-------
SECTION 3
RECOMMENDATIONS
Since this research program indicated that substantial levels of volatile
Priority Pollutants are present in the off-gas from aeration basins, it is
recommended that additional studies be conducted with other wastewater
treatment facilities. Wastewater treatment facilities that receive predomi-
nantly industrial and municipal wastewater should be investigated since the
facility investigated here receives 40% industrial/60% municipal sewage.
Additional research is needed to determine the identity of chlorinated
organics produced via superchlorination of sludge. Since approximately 3%
of the organics in effluent sludge from a superchlorination process was
chlorinated and only a small fraction was detected by capillary GC/NICI-
MS/COMP, it is recommended that the non-volatile fraction be characterized
by ancillary techniques. Very little information exists concerning the
identity, toxicity, and mutagenicity of the chlorinated organics.
-------
SECTION k
PROGRAM OBJECTIVES
This research program, the first of its kind, had the following broad
objectives:
(1) confirm the quantitative capabilities of the previously developed
and validated sampling apparatus and analytical procedure for
measuring volatiles from aeration basins at Wastewater Treatment
Facilities;
(2) develop liquid and gas sampling strategies to provide a representa-
tive analysis of the loss of volatiles from aeration basins;
(3) consider factors such as geometry, liquid flow pattern, and air
flow pattern to determine the optimum sampling strategy;
(4) analyze both liquid and off-gas for volatile Priority Pollutants;
(5) measure equilibrium partition of several compounds between the
liquid, solid and gas phase;
(6) conduct sampling and analysis of vapors produced by stabilization
of sludge by superchlorination;
and (7) relate concentrations in off-gas to system and wastewater characteris-
tics, if possible.
The results obtained from the research on each of the above objectives
would serve to fully verify a field-tested procedure and a body of data
relating the concentration of Priority Pollutants in the aeration system
off-gas to the system and wastewater characteristics.
-------
SECTION 5
PARTITIONING OF "PURGEABLE" PRIORITY POLLUTANTS BETWEEN
AQUEOUS AND SOLID PHASES IN ACTIVATED SLUDGE SAMPLES
INTRODUCTION
It would be desirable to predict the concentration of volatile organics
in the off-gas from aeration basins based on the concentrations measured in
the liquid phase. Measurements of volatile organics in liquid samples
present fewer problems with the mechanics of sample acquisition from the
treatment facility. However, in order to successfully predict the concen-
tration of volatiles in the off-gas, it is necessary to recognize and
understand the potential equilibria of pollutants between the solid, liquid
and gas phases such as in the aeration of activated sludge. Figure 1 de-
picts the relationships between these three phases and a given input rate of
a chemical.
GAS
Figure 1. Potential gas-liquid-solid equilibria in aeration basin.
The material balance equation for a chemical in the above schematic of
interactions in an aeration basin is given by:
dC
-j-^ = kT - k_SCu + kTSC_ - k-AO,
dt I SW LS GW
where V = volume of water
A = surface area of the water in the basin
(1)
8
-------
S = weight of the solid
Cr, = concentration of the chemical in water
W
k = rate constants (I = input, S = sorption to solid, L = desorp-
tion, G = vaporization)
Cc = concentration of the chemical in the solid
S
If a chemical has a kT/kc ratio » 1, then the relationship can be simpli-
.L o
fied to VdC.Vdt = k,-kf,ACu. Using Henry's Law one can approximate the rate
W X u W
of volatization of the chemical:
dC
- -dl = KiL
-------
EXPERIMENTAL
Description of Treatment Plant
The plant selected for characterization of sorption phenomena and the
measurement of Priority Pollutant levels in the off-gas was the Northside
Treatment Plant in Durham, NC. The Northside Treatment Plant treats raw
wastewater from homes, businesses and industries in the northeast side of
Durham. It receives approximately 40% industrial and 60% municipal sewage.
Typical flow is 23.8 million liters/day. A diagram of this plant is shown
in Figure 2. The major units include: (1) core 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 a 4 to 6 h detention and forced air
diffusion (observation of the tanks indicates that the flow pattern is arbi-
trary somewhere between plug flow and complete vertical and partial lateral
mixing); (6) secondary sedimentation with sludge recycle; (7) chlorination;
and (8) anaerobic sludge digestion.
The areation tanks are each 4.5 x 60.96 m with a depth of 3.96 m.
Liquid depth is ~3.5 m. Air is injected into each tank by 344 porous plates,
30.4 cm x 304 cm, set vertically in double rows in a header placed 30.4 cm
above the tank bottom. There is a total of 9 aeration tanks at this facility.
Materials
14
C-Radiolabeled chlorobenzene, toluene, benzene, chloroform, trichloro-
ethylene, bromobenzene and carbon tetrachloride were obtained from New
England Nuclear (Boston, MA). Scintillation cocktail containing 250 raL of
Triton X, 750 mL toluene, and 4.5 g of Omnifluor was prepared. Aliquots of
the sample were added to 15 mL of scintillation cocktail and radioactivity
was determined on a Packard Tricarb 3375 liquid scintillation spectrometer.
The radiotracer was counted until a standard error of 2.5 was obtained.
Observed radioactivity was corrected for quenching by the external standard
ratio method and all counts/min (CPM) were converted to disintegrations/min
(DPM).
Samples
Samples collected for this study are given in Tables 1 and 2 and their
locations in Figure 2. Samples were also collected of raw wastewater entering
10
-------
1 FINAL
feLTTtlNG
1 TANK&
,
t
AT9
AtPMTION TlkNKS AT 8
AT 7
**J BtTURM" ACtlV*ttO SLUOGI^
FIMAL
MTTLING
TANKS
.......
| — ^
SLUOGt- CONOITIONINO
ATS
AT4
MOATION
L3 L2
TANKS
LI
1
tffl-UtNT
TO HIVI.B
•«— RAW StW»OL rBOM CITY-
UIGM QJkTL riLTLtt \ /MIGU Q*TL TILTtQ
i 1 I NO. 2
SLUOOL
DOVING
Figure 2. Flow diagram of Northside Treatment Sewage Plant, Durham, NC. (Pilot Study: sampling
at LI and L3 only; Study No. 1: sampling at LI and L3 only; Study No. 2: sampling at
LI, L2 and L3).
-------
Table 1. SAMPLING PARAMETERS FOR ACTIVATED SLUDGE:
NORTHSIDE TREATMENT PLANT, DURHAM, NCa
PILOT STUDY -
Sampling Period No.
Sampling Time
lb
2b
3
4,
5b
1250-1305 h
1345-1400 h
1505-1525 h
1600-1615 h
1720-1740 h
Samples taken concurrently with off-gas samples described in
Section 6 (Table 11).
Samples collected for sorption studies, other samples also collected
for determining "purgeable" Priority Pollutants in activated sludge
(see Section 6, Table 11). Samples of sludge were collected from
location No. 1 in aeration tank No. 2 (AT2, Fig. 2) on August 19,
1979.
12
-------
Table 2. SAMPLING PARAMETERS FOR ACTIVATED SLUDGE: STUDY NO. 2 -
NORTHSIDE TREATMENT PLANT, DURHAM, NCa
LI
lb 1200 h
2 1300 h
3 1400 h
4 1500 h
5b 1600 h
Location
L2
1210 h
1310 h
1410 h
1510 h
1610 h
L3
1220 h
1320 h
1420 h
1520 h
1620 h
r*
Samples taken concurrently with off-gas samples described in Section 6
(Table 12).
Samples collected for sorption studies, other samples also collected
for determining "purgeable" Priority Pollutants in activated sludge
(see Section 6, Table 12). Samples were taken from AT2 (Fig. 2) on
January 29, and again on May 14, 1980. Raw wastewater was also
collected at 1130 on May 14, 1980.
13
-------
into the Northside Treatment Plant (Durham, NC) and at specified points of
monitoring for Priority Pollutants in aeration gases.
Sampling Materials and Methods
Liquid samples from the aeration basins and the incoming raw wastewater
were scooped with a 1 L beaker and transferred via a glass funnel to a 1 L
®
narrow mouth glass amber bottle with Teflon -lined cap. The glass funnel
was washed with deionized-distilled water after each sample duplicate had
been collected. All glassware was prewashed with nondetergent soap, rinsed
with deionized-distilled water, and dried in an infrared oven and baked in
an oven at 450°C for 2 h. Samples collected were placed on ice, transported
back to the laboratory and stored at 4°C until ready for use in experiments.
Equilibration Time
In order to determine the time required to achieve equilibrium conditions
for Priority Pollutants between the liquid and solid phases, a duplicate
study was conducted. One |JL of radiolabelled halogenated aromatics in
methanol was added to 10 mL of activated sludge and equilibrated for 30 min
®
and 18 h at 4°C with magnetic stirring in 50 mL centrifuge tubes (Teflon -
lined caps). In each experiment, approximately 200 ng of C-bromobenzene
14
and 750 ng of C-chlorobenzene were used. After equilibration, the solids
were removed by slow speed centrifugation ("^500 rpm) and 1.0 mL aliquots of
the supernatant were transferred to 15 mL of toluene/Omnifluor/Triton X
cocktails and the radioactivity determined. An aliquot of the solids was
also measured for radioactivity. The DPMs were normalized against a single
measured volume for comparison. Equal amounts of spiking solutions were
added to blank cocktails to serve as recovery standards.
Data in Table 3 reflect the disparity in sorption at the low concen-
tration level for the 30 min study. Approximately 65 to 66% of the chloro-
benzene and bromobenzene were recovered in the liquid phase after centrifuga-
tion and removal of the solid phase. A second experiment was conducted with
an equilibration temperature and time of 4° for 18 h, respectively (Table
4). These results indicate that the sorption of chlorobenzene and bromoben-
zene to the solid phase does not increase with time. Sorption of the Priority
Pollutant to the solid phase occurs rather rapidly under the vigorous mixing
conditions and an apparent equilibrium is reached between the surface of the
14
-------
Table 3. ADSORPTION OF CHLOROBENZENE AND
BROMOBENZENE TO ACTIVATED SLUDGE3
Percent Recovered + S.D.
Compound Liquid Phase Solid Phase
Chlorobenzene 66+1.0 34+1.0
Bromobenzene 65+0.5 35+1.0
a30 min equilibration @ 4°C.
Solid phase was 30 mg/mL of total sludge.
Table 4. ADSORPTION OF CHLOROBENZENE AND
BROMOBENZENE TO ACTIVATED SLUDGE3
Compound
Chlorobenzene
Bromobenzene
Liquid
65
65 +
Percent Recovered + S.D.
Phase Solid Phase
35
0.5 35 + 1.0
o
18 h equilibration @ 4°C.
Solid phase was 30 mg/mL of total sludge.
15
-------
solid matrix and liquid phase. However, this study does not indicate
whether a very long time period is needed for the sorption of the chloroben-
zene or bromobenzene into the micropore structure of the solid matrix. In
all subsequent experiments, equilibration was allowed to proceed for 18 h
at 4°C to preserve the integrity of the sludge.
Aqueous-Solid Sorption Studies
Measurements of adsorptive properties of a chemical to a solid particle
can be described by adsorption isotherms which relate the concentration of
the chemical in the aqueous phase (C ) and the concentration on the solid
phase (Cg) at equilibrium. These units may be expressed in |Jg/L and [Jg/g.
The adsorption of radiolabeled Priority Pollutants to the solids in acti-
vated sludge were expressed by the Freundlich equation. The Freundlich
adsorption isotherm is an empirical equation which gives the most general
description of a variety of relationships:
Cg = KCw or log Cg = log K + n log GW (4)
where K (or log K) and n are the important parameters of adsorption strength
and shape of the curve. Using double log plots of the measured equilibrium
concentrations, the actual values of n and log K can be determined where n
is the slope and log K the intercept of the line. When n approaches unity,
the amount adsorbed is then proportional to the water concentration. Thus,
the magnitude of the intercept is an indicator of adsorption capacity and
the slope of adsorption intensity.
The data obtained by measuring the quantity of radiolabeled compounds
distributed between the liquid and solid phases were subjected to a linear
regression analysis according to the above equation. Each data point for
linear regression analysis constituted at a minimum a triplicate determination
of the distribution of the radiochemical between the solid and liquid phases.
Effect of Carrier Volume on Sorption--
The effect of the spiking carrier volume on the sorption of benzene to
activated sludge was examined at 3 different concentrations of benzene
(Table 5). Methanol was the carrier solvent in both cases. Benzene at 1,
100 and 1500 ppb was used in combination with spiking volumes of 50 and
1,000 |jL. It is evident from these data that perhaps at low levels, i-£-> 1
ppb, the use of excessive amounts of carrier solvent might compete with the
16
-------
Table 5. EFFECT OF SPIKING CARRIER VOLUME ON FREUNDLICH ADSORPTION ISOTHERM PARAMETERS FOR
BENZENE IN ACTIVATED SLUDGE3
Spiking Vol.
(ML)
50
1000
Initial Cone.
(Mg/L)
1
100
1500
1
100
1500
LogCw
-0.357
1.732
3.100
-0.229
1.771
3.090
Log Cs
0.271
2.186
2.903
0.136
2.136
2.954
c.
\
J
1
Slope
n
0.774
0.861
Intercept Corr. Coef.
Log K (K) r
0.63 (4.27) 0.991
0.41 (2.57) 0.993
aSamples were taken as part of pilot study - Northside Treatment Plant, Durham, NC (August 19, 1979)
-------
Priority Pollutant for sorption to the solid matrix. Increasing the spiking
volume of solvent from 50 to 1000 pL reduced the sorption capacity by 40%
(Table 5). In all subsequent experiments, where possible, 50 pL of carrier
solvent, methanol, was employed.
The preparation of standard and sample cocktails for this and subsequent
experiments was as described above with one modification: aqueous phases
were obtained by gravity settling instead of centrifugation.
Normalization of liquid volumes was employed in order to allow for
comparing information between experiments. The liquid volume was measured
after pipetting a 1.0 mL aliquot to the scintillation cocktail by decanting
the remaining supernatant liquid into a graduated cylinder. A net sludge
volume of 0.82 + 0.27 mL was obtained and normalization values were determined
by the difference between this value and the spiking volume (9.23 for 50 pL
spikes, 10.18 for 1.0 mL volume spikes). A composite (pooled) liquid volume
was obtained for 50 pLspiking. The normalization factor was then obtained
(9.11) which was not significantly different from the value for previous
experiments. Thus, the uncertainties of normalization were not propagated
in the sorption studies.
Sorption of Selected Priority Pollutants—
The purpose of these experiments was to determine whether significant
changes occurred with time and location within the aeration tanks of the
adsorption capacity (and intensity) of activated sludge for Priority Pollu-
tants. If the simple relationship described by equation 3 is to be used for
predicting the concentration of Priority Pollutants in the off-gas stream,
then the concentration determined in the liquid phase must be relatively
independent of sorption to the solid phase. Sorption would perturb the
distribution of Priority Pollutants between the liquid and gas phases. It
follows that the adsorption capacities and intensities must be relatively
small or that the mass transfer coefficient be measured for each case to use
eq. 3.
The sorption of several Priority Pollutants to activated sludge as a
function of concentration for the Pilot Study is given in Table 6. The
various adsorption isotherm parameters have been tabulated for reference.
The initial concentration for each of the chemicals is indicated as well as
18
-------
VO
Table 6. FREUNDLICH ADSORPTION ISOTHERM PARAMETERS: SELECTED PRIORITY POLLUTANTS
IN ACTIVATED SLUDGE - PILOT STUDY AT NORTHSIDE TREATMENT FACILITY, DURHAM, NC
Compound
Chloroform
Benzene
Chlorobenzene
Toluene
Initial Cone.
Mg/L
1.1
10.9
54.4
2.0
48.9
99.6
1.9
48.8
97.6
2.0
49.8
99.6
Log C
& w
-0.119
1.037
1.699
-0.009
1.379
1.739
0.027
1.540
1.898
0.121
1.369
1.791
Slope Intercept
Log C n Log K (K)
s
0.060 >v
0 \ 0.532 -0.06 (0.87)
1.161 J
0.531 *\
1.920 \ 0.957 0.55 (3.5)
2.174 J
0.445 ^
1.674 { 0.747 0.44 (2.75)
1.791 J
0.355 <^
1.944 \ 1.036 0.29 (1.94)
1.968 J
Corr. Coef.
r
0.748
0.999
0.995
0.973
-------
log C.,, log Cg, the slope (n), intercept (log K, K) and the correlation
coefficient for the linear regression. The initial concentration chosen for
all of the sorption studies was based on preliminary data on levels of
Priority Pollutants in activated sludge (1). These levels were generally 1
to 100 ppb.
Of the four chemicals employed in this study, benzene exhibited the
highest adsorption capacity (K = 3.5). It is interesting to compare this
value with that found for its adsorption to carbon where the reported K
value was 1 (2). In contrast the K value for chloroform was considerably
less than that reported for its adsorption to carbon. The adsorption capa-
city of chlorobenzene and toluene for carbon is reported as 91 and 26,
respectively (2). A comparison of the K values for carbon with activated
sludge indicates that the adsorption capacity is considerably lower in
activated sludge.
In the first of two experiments, 10 ml of each total sludge sample was
pipetted into a 50 mL centrifuge tube containing a magnetic stirrer. The
sludge was magnetically stirred to provide good mixing of the sample. Fifty
[JL of radioisotope in methanol solution was pipetted directly onto the
surface interface such that initial concentrations of 5, 50 and 100 ppb were
achieved (0.05, 0.50, and 1.0 (Jg/10 mL). The tubes were then sealed with
®
glass stoppers or Teflon -lined caps and transferred to a cold room at 4°C.
The samples were stirred for 16 h, pipetted into 15 mL graduated conical
centrifuge tubes and let stand for 2 h. Aliquots were then transferred to
a Triton X/toluene/Omnifluor scintillation cocktail for counting of the
radioisotope. The solid volume was recorded to +0.05 mL to obtain the total
liquid volume necessary for the normalization of the scintillation radioiso-
topic data.
The results for aqueous-solid sorption experiment No. 1 for activated
sludge are given in Table 7. The adsorption isotherm parameters for the
selected Priority Pollutants were determined at time periods 1 and 2 (see
Table 2) at three locations in the aeration tank No. 2 (see Figure 1). All
data were results of triplicate analysis for each concentration, period, and
location. The data in Table 7 indicate significant differences in the
adsorption capacity for Priority Pollutants both with respect to time and
20
-------
Table 7. FREUNDLICH ADSORPTION ISOTHERM PARAMETERS FOR SELECTED PRIORITY POLLUTANTS IN
ACTIVATED SLUDGE: NORTHSIDE TREATMENT PLANT, DURHAM, NC - EXPERIMENT NO. 1 .
to
Initial Cone.
Compound Period Location |Jg/L
Chloroform 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
Carbon tetrachloride 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
LogCw
0.432
1.253
1.746
0.512
1.536
1.754
0.441
1.521
1.797
0.455
1.438
1.783
0.498
1.438
1.811
0.538
1.470
1.608
-0.154
0.651
1.253
0
1.059
1.228
0.231
1.111
0.965
Slope
Log Cs n
0.894 -N
2.026 J 1.002
2.164 J
0.766^
1.711 } 1.057
2.154 J
0.788"»
1.634 > 0.828
1.935J
0.855*}
1.873 ) 0.890
1.983J
0.894^
1.873 \ 0.921
2.065J
0.583 "\
1.743 > 1.435
2.236 J
1.156^
2.179 } 0.929
2.435J
1.125^
2.107 } 1.020
2.440J
0.985^
2.044 > 1.458
2.442J
Intercept
Log K (K)
0.55 (3.54)
0.20 (1.58)
0.41 (2.57)
0.48 (3.02)
0.46 (2.88)
-0.21 (0.62)
1.38 (23.9)
1.11 (12.9)
0.70 (5.01)
Corr. Coef.
r
0.961
0.988
0.998
0.987
0.992
0.985
0.969
0.993
0.912
(continued)
-------
Table 7 (cont'd.)
K>
N>
Initial Cone.
Compound Period Location gg/L
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
Chlorobenzene 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
LogCw
-0.046
0.697
1.320
0.061
0.901
1.396
-0.161
0.942
1.243
0.447
1.468
1.489
0.243
1.438
1.776
0.441
1.420
1.784
0.362
1.253
1.705
0.484
1.277
2.761
0.476
1.255
1.672
Slope
Log Cs n
1.186 "^
2.174 1 0.915
2.418 J
1.108 ^
2.144 ) 0.993
2.396 J
1.115 "^
2.095 I 0.905
2.396 J
0.865^
1.833 } 1.201
2.360J
1.035^
1.873 ) 0.707
2.123 J
0.788*^
1.820 > 0.945
2.019J
0.954^
2.026 > 0.973
2.211 J
0.813*^
2.012 > 0.521
2.144J
0.730^
1.972 } 1.260
2.178J
Intercept
Log K (K)
1.32 (20.9)
1.10 (12.6)
1.26 (18.2)
0.32 (2.09)
0.86 (7.24)
0.39 (2.45)
0.65 (4.47)
0.87 (7.41)
0.19 (1.55)
Corr. Loef.
r
0.960
0.982
0.999
0.944
0.999
0.993
0.980
0.821
0.976
(continued)
-------
Table 7 (cont'd.)
Initial Cone.
Compound Period Location vg/L
Toluene 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
Benzene 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
Log Cw
0.114
1.360
1.600
0.423
1.413
1.688
0.419
1.379
1.672
0.398
1.378
1.542
0.255
2.396
1.736
0.335
1.243
1.618
0.431
1.202
1.144
0.455
1.421
1.776
0.419
1.380
1.672
Slope
Log Cs n
1.091 "^
1.953 / 0.773
2.299 J
0 . 894 *\
1.901 ) 1.045
2.228 J
0.819^
1.868 > 1.087
2.178 J
0.921 "^
1.936 \ 1.166
2 . 334 J
1.028^
1.919 } 0.484
2.245 J
0.910*^
1.979 > 1.055
2.228 J
0.885^
2.053 > 1.805
2.455 J
0.855 ^
1.369 } 0.557
1.599 J
1.130^
1.919 } 0.914
2.314 J
Intercept
Log K (K)
0.99 (9.77)
0.45 (2.82)
0.36 (2.29)
0.44 (2.75)
1.022 (10.5)
0.58 (3.80)
0.13 (1.35)
0.59 (3.89)
0.73 (5.37)
Corr. Coef.
r
0.991
0.999
0.999
0.990
0.843
0.994
0.950
0.999
0.994
(continued)
-------
Table 7 (cont'd.)
K5
Initial Cone.
Compound Period Location Hg/L
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
Trichloroethylene 1 1 5.0
49.8
99.5
1 2 5.0
49.8
99.5
1 3 4.6
46.1
92.2
2 1 5.0
49.8
99.5
2 2 5.0
49.8
99.5
2 3 4.6
46.1
92.2
Log Cv
0.255
1.429
1.722
0.477
1.241
1.516
0.403
1.435
1.618
-0.155
1.077
1.413
0.615
1.331
1.621
0.344
1.220
1.577
0.079
1.202
1.631
0.491
1.310
1.475
0.254
1.079
1.618
Slope
Log C n
1.028 "N
1.883 \ 0.775
2.193 J
0.824 ^
2.033 ) 1.491
2 . 347 J
0 . 839 ""»
1.799 / 1.071
2.228 J
1.156 ^
2.101 } 0.782
2.390 J
1.021 *\
1.976 } 1.270
2.284 J
0.902°^
1.919 ) 1.111
2.258J
1.103^
2.053 ) 0.775
2.277 J
0.802"^
1.991 } 1.545
2.366J
0.971%
2.056 } 0.954
2.228 J
Intercept
Log t. W
0.82 (6.61)
0.13 (1.35)
0.39 (2.45)
1.27 (18.6)
0.25 (1.78)
0.53 (3.39)
1.05 (11.2)
0.03 (1.07)
0.81 (6.46)
Corr. Coef.
r
0.997
0.988
0.986
0.999
0.999
0.999
0.996
0.997
0.962
-------
location in the aeration tank. For example, the variations in the K values
for chloroform ranged from 0.62 to 3.54. Data for other Priority Pollutants
(Table 8) show similar trends. Also, the sorption intensity (n) for several
chemicals varies by as much as a factor of 3.
In order to more clearly demonstrate this variation, the mean value,
standard deviation, and coefficient of variation were calculated for the
sorption intensity (n) and sorption capacity (K) for time periods 1 and 2 of
experiment No. 1. These data are given in Table 8. Inspection of the
coefficients of variation (given in parenthesis) for each chemical's mean
value of n and K indicates a large variation within the three sampling loca-
tions of aeration tank No. 2. Table 9 gives the variation of the adsorption
isotherm parameters for all data listed in Table 8. Although the statistical
accuracy for the adsorption intensity and capacity of these selected Priority
Pollutants for the solids in activated sludge is greater than the individual
data given in Table 8, the variation as expressed by the coefficient of
variation is large. These results probably imply that the sorption of
volatile chemicals to the solid phase in activated sludge cannot be ignored
when attempting to predict their concentration in the off-gas by using
liquid phase concentrations.
A comparison of the adsorption isotherm parameters for raw wastewater
with activated sludge clearly indicates that the adsorption capacity for the
chemicals studied is negligible in raw wastewater (Table 10). The sorption
intensity for benzene, chlorobenzene, chloroform and toluene for activated
sludge in experiment No. 2 is comparable to the values observed in previous
experiments. A slightly larger disparity in the K values was observed
between the two sets of data (compare Tables 6 and 10).
25
-------
N>
Table 8. VARIATION OF FREUNDLICH ADSORPTION ISOTHERM PARAMETERS FOR SELECTED
PRIORITY POLLUTANTS IN ACTIVATED SLUDGE3
Period 1
Period 2
Compound
K
K
Chloroform 0.962 + 0.119 (12) 2.40 + 1.51 (63) 1.082 + 0.306 (28) 1.74 + 2.45 (141)
Carbon tetrachloride 1.136 + 0.283 (25) 11.5 + 2.19 (19) 0.938 + 0.048 (5) 16.9 + 1.29 (8)
Chlorobenzene 0.951 + 0.247 (26) 3.31 + 1.95 (60) 0.918 + 0.373 (41) 3.71 + 2.24 (60)
0.968 + 0.170 (18) 3.98 + 2.19 (55) 0.902 + 0.366 (41) 4.78 + 1.99 (42)
1.092 + 0.643 (59) 3.02 + 2.04 (68) 1.112 + 0.360 (32) 2.82 + 2.24 (79)
1.054 + 0.249 (24) 4.79 + 3.39 (71) 1.091 + 0.403 (37) 4.27 + 3.47 (81)
Toluene
Benzene
Trichloroethylene
Mean values + S.D. (C.V.) for n and K were calculated for locations 1 through 3 in Table (7).
-------
Table 9. VARIATION OF FREUNDLICH ADSORPTION ISOTHERM PARAMETERS
FOR SELECTED PRIORITY POLLUTANTS IN ACTIVATED SLUDGE -
MEAN + S.D. (C.V.) FOR ALL DATA IN TABLE 7
Compound n k
Chloroform 1.022 + 0.218 (21) 2.04 + 1.91 (93)
Carbon tetrachloride 1.037 + 0.211 (20) 13.8 + 1.74 (13)
Chlorobenzene 0.934 + 0.283 (30) 3.54 + 1.95 (55)
Toluene 0.935 + 0.258 (28) 4.36 + 1.95 (45)
Benzene 1.102 + 0.466 (42) 2.88 + 1.99 (69)
Trichloroethylene 1.073 + 0.300 (28) 4.57 + 3.02 (66)
27
-------
Table 10. COMPARISON OF FREUNDLICH ADSORPTION ISOTHERM PARAMETERS FOR SELECTED
PRIORITY POLLUTANTS IN RAW WASTEWATER INFLUENT WITH ACTIVATED SLUDGE: NORTHSIDE TREATMENT
PLANT, DURHAM, NC - EXPERIMENT NO. 2
Compound
Benzene
Chlorobenzene
Chloroform
Toluene
Initial Cone.
ug/L
1.99
49.8
99.6
1.94
48.8
97.6
1.10
10.9
54.4
1.99
49.8
99.6
Log Cw
0.272
1.67S
1.943
0.288
1.688
1.989
0.040
1.037
1.736
0.299
1.697
1.998
Raw Wastewater Influent
Slope Intercept Corr. Coef.
Log Cs n Log K (K) r
1
2
0
0
0
0
0
0
0
2
2
.697 1 1.112 0.04 0.982
-378J
> 0 0 1.0
>0 0 1.0
.32 \ 1.550 -0.44 0.996
.55 J
Activated Sludge
LogCw
-0.020
1.387
1.998
-0.224
1.533
1.898
-0.120
1.037
1.736
0.118
1.369
1.998
Slope
Log GS n
0.538 0.842
2.174 J
0.454 *\
1.688 > 0.653
1.791 J
0.056 "^
0 ) 0.556
1.213 J
0.353 «^
1.944 } 0.978
2.101 J
Intercept Corr. Coef.
Log K (K) r
0.60 (3.98) 0.987
0.61 (4.07) 0.996
0.07 (1.17) 0.761
0.33 (2.14) 0.968
00
-------
SECTION 6
ESTIMATION OF PURGEABLE PRIORITY POLLUTANT LEVELS IN AIRSTREAMS
FROM ACTIVATED SLUDGE
INTRODUCTION
Studies were conducted to determine the levels of purgeable Priority
Pollutants in raw wastewater, activated sludge and in the off-gas from
activated sludge basins stripped by the aeration process. The objective was
to determine the relationship between off-gas concentrations between the
front and end of an aeration basin to the concentrations for the same Priority
Pollutants in activated sludge collected at the beginning and end of an
aeration basin. Furthermore, the significance of the sorption data from
Section 5 was to be considered in relating off-gas concentrations to the
concentrations of Priority Pollutants in activated sludge. In order to
demonstrate this phenomen liquid and air samples were collected simultaneously
at several points across an aeration basin.
An additional objective was to delineate the steps necessary to calculate
the emission rate for Priority Pollutants as the result of the off-gassing
from aeration basins in a wastewater treatment facility. In order to conduct
studies to address these two objectives, the Northside Wastewater Treatment
plant in Durham, NC which receives a mixture of industrial and municipal raw
sewage was selected for this study.
EXPERIMENTAL
Sampling System
The design and fabrication of a Nutech sampler has been previously
described (1). The Nutech sampler (Fig. 3) was designed for sampling of
"purgeable" organic Priority Pollutants during gas evolution from aeration
tanks and grit chambers at wastewater treatment facilities.
The aeration tank may be considered a surface source of nonhomogeneous
character where the rate of gas evolution and the concentration of organics
29
-------
SOLENOID VALVE
j SWITCHES
• ^METERING VALVES
DRY CAS METER
DIGITAL DISPLAY.
TEMP/MASS FLOW
READOUT SWFTCH
POWER AND PUMP
SWITCHES
CONTROL CONSOLE
Figure 3. Schematic of sampler system for grit chambers and
aeration tanks.
30
-------
varies from point to point. Time dependence in plug flow and other variabi-
lities may also be expected. Obtaining meaningful data under these conditions
requires that the total volume of gas evolving from the surface be determined.
The sampling head (Fig. 4) which was designed for this sampler defines a
certain surface area and channels all the gases emitted through the appro-
priate flow monitors. A skirt extends into the liquid (Fig. 4) and defines
a source area and provides a low pressure buildup to force the gas through
the sampler. For air to liquid (v/v) ratios for typical aeration tanks such
as the one at the Northside Treatment plant in Durham, NC, a surface area of
2
0.365 m should evolve a gas flow within the range of 1 to 30 L/min. The
sampling head was designed as a rectangle instead of a square to more represen-
tatively capture the off-gas across the tank, thus minimizing variation of
emission from center where the diffusors are located to the side of a typical
aeration tank.
The initial step in this procedure was selecting an appropriate location
for the sampling head and console. The tank design and operation varies
considerably from plant to plant. Care was exercised to place the units
where sufficient bubble activity was present and where the console and
sample head were located within a few feet of each other and within reach of
AC power. Three sampling heads and consoles were secured at three locations
of aeration tank No. 2 (see Fig. 2) by attaching the support arm to a railing
and, for additional stability, attaching ropes to the eyebolts located at the
ends of each of the sampling heads.
2
Typical aeration rates in the tanks were in the range of 26.9 L/min/m
of surface area. This rate was determined by passing the total flow through
the dry gas meter (Fig. 5) for a short period of time, i^.e. , about 10 min.
During this period the umbilical line and cartridge chamber were stabilized
to the operating temperature of 40°C.
Flow through individual cartridge holders (a triplicate set was collected)
was set by adjustment of the metering valve (Fig. 5). 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
31
-------
_ >8 HOLES m},," CENTERS,
FULL LENGTH
CO
36
J/4 X1% ,5 TAB, WELD TO INTERIOR PLATE, DRILL AND TAP FOR 6-32 SS
SCREW, POSITION AND NUMBER AS REQUIRED , BEND AS SHOWN.
3/4 x % SS WB • *El-D TO INTERIOR ANGLE , DRILL AND TAP FOR 6-32 SS
Figure 4. Schematic of sampling shroud.
-------
HEADED UMBILICAL
CARTRIDGE MANIFOLD
EXHAUST
EXHAUST
VALVE ** OUT! MN
MASS FLOW
METER
Figure 5. Diagram of pneumatics in sampler system.
33
-------
flow through each holder. When the flow rates had been set to the desired
level, the solenoid valves were shutoff without disturbing flow settings
and the prepared cartridges were installed for sampling (1).
The mass flow control units of the Nutech 851 samplers, capable of
triplicate or quadruplicate cartridge sampling, had been calibrated against
a bubble flow meter attached to the main pump exhaust. A linear relationship
with an intercept of 0 and a slope deviation from unity of <15% was observed
for all of the mass flow channels.
Sample Collection/Strategy
Three studies (a pilot and two experiments) were conducted at the
Northside Treatment Plant in Durham, NC. Air and liquid samples were
collected at two or three locations of the aeration tanks as shown in
Figure 2 for each study. Sampling was conducted over a 4.5 h period
(approximating hydraulic plug flow) for the Priority Pollutants present in
the airstream leaving the activated sludge basin. Samplers were placed at
different points along the second aeration basin to determine whether a
concentration gradient of Priority Pollutants could be detected in the off-
gas between the front and backends of the tank. Simultaneously, liquid
samples were collected at the same locations as air, sampling at various
time intervals throughout the 4.5 h period.
In the pilot study a triplicate set of air samples was obtained from
the second basin at the influent end, and a quadruplicate set near the
effluent end (Fig. 2). Grab liquid sludge samples were taken in duplicate
from the first, second, fourth, sixth and eighth aeration basins at the
beginning and end of the air sampling period (Table 11). Samples were
§
transferred to 60 mL amber bottles sealed with Teflon -lined caps, stored on
ice in the field and then transferred to a cold room at 4°C upon arrival at
the laboratory.
In experiments No. 1 and 2 sampling was conducted of the air streams
leaving the activated sludge basin at three locations (beginning, middle and
end). Two sampling periods were employed covering a total of 4.5 h (Table
12). Triplicate samples of the air stream leaving aeration tank No. 2 were
taken at each location during the two time periods (Fig. 2). Concurrently
at the beginning, middle and end of the air sampling period, activated
34
-------
Table 11. SAMPLING PROTOCOL FOR AIR AND SLUDGE SAMPLES: PILOT STUDY -
NORTHSIDE TREATMENT PLANT, DURHAM, NC
co
Air Samples
Aeration Tank Volume
No. Period Time Location Cartridge (L)
1 _____
2 1 1300-1730 LI Tl 2.05
T2 2.03
T3 1.95
1 1300-1730 L3 Tl 2.07
T2 2.02
T3 1.98
4 _____
6 _____
8 _ _ _ _ _
Sludge Samples
Period
1
5
1
2
3
4
5
1
5
1
5
1
5
Time
1250
1740
1305
1345
1505
1600
1735
1255
1730
1300
1725
1305
1720
-------
Table 12. SAMPLING PROTOCOLS FOR AIR, ACTIVATED SLUDGE AND RAW WASTEWATER SAMPLES:
EXPERIMENTS 1 & 2 - NORTHSIDE TREATMENT PLANT, DURHAM, NC
Activated Sludge
Samples
Air Samples (Aeration Tanks)
Raw Wastewater
Samples
Experiment
No.3 LI
1
2
1200
1300
1400
1500
1600
1200
1300
1400
1500
1600
L2
1210b
1310b
1410b
1510b
1610b
1210
1310
1410
1510
1610
Period
L3 No. Time
1220 1
1320
1420
1520 2
1620
1220 1
1320
1420
1520 2
1620
1200-1415
1200-1415
1200-1415
1415-1630
1415-1630
1415-1630
1200-1415
1200-1415
1200-1415
1415-1630
1415-1630
1415-1630
Location Cartridges
LI
L2
L3
LI
L2
L3
LI
L2
L3
LI
L2
L3
Tl
Tl
Tl
Tl
Tl
Tl
Tl
Tl
Tl
Tl
Tl
Tl
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T2
,T3
,T3,T4
,T3,T4
,T3
,T3,T4
,T3,T4
,T3
,T3,T4
,T3,T4
,T3
,T3,T4
,T3,T4
Volume
(L)
1.87 +
1.76 +
1.81 +
1.94 +
1.58 +
1.81 +
1.80 +
1.75 +
1.73 +
1.80 +
1.80 +
1.75 +
.07
.22
.09
.18
.20
.16
.08
.07
.09
.09
.13
.17
Time
1305
1400
1525
1615
1740
1130C
Experiments No. 1 and 2 were conducted on January 29, and May 14, 1980, respectively. Air and
sludge samples were taken at activated sludge aeration tank Nos. 2 and 4 for Expts. No. 1 and 2,
respectively.
DNot analyzed for "purgeable" Priority Pollutants.
"Collected only for sorption studies.
-------
sludge samples were taken from the same locations in this tank (Table 2).
Table 12 gives the sampling parameters for both experiments.
In the second experiment raw wastewater and samples of ambient air
leaving aeration tank No. 2 were taken over a 4.5 h period. Again three
2
flotation heads of 0.365 m dimensions were placed at the initial, middle
and final sites of plug flow in aeration tank No. 2 (see Fig. 2). The mass
flow controllers were set at 13 mL/min via previously established mass
flow/exhaust flow calibration curves. Triplicate samples were adsorbed onto
1.5 cm x 6.0 cm Tenax cartridges for 2 h and 15 min each. The cartridges
were then replaced with a second set and sampling continued for the remaining
period of time (see Table 12). Activated sludge samples from three locations
along aeration tank No. 2 were also taken in duplicate approximately every
hour.
Volatile Organic Analysis (Sludge and Wastewater)
The purging method as described in the EPA Protocol for Sludge was
utilized (5). Pooling of three aqueous samples gave an average dry solid
sludge concentration of 3 mg/mL. Although such a solid concentration would
be well below an established EPA Protocol gradient (50 mg/10 ml for an
undiluted sample) an arbitrary dilution of 1:10 with distilled water was
employed to avoid possible saturation during GC/MS analysis.
The diluted suspensions were purged with helium at 40 mL/min for 12 min
onto a 1.5 cm x 6.0 cm 30/60 mesh Tenax cartridge as previously described
(5). Samples were stored over activated calcium sulfate with the addition
of external standards (perfluorotoluene and perfluorobenzene) and then
submitted to GC/MS for analysis.
Air Samples
Tenax cartridges were stored over activated calcium sulfate overnight.
Internal standards of perfluorobenzene and perfluorotoluene (^400 ng) were
loaded on each cartridge and samples were analyzed by GC/MS. The procedures
employed were as previously described (1).
Quality Control and Quality Assurance
Reagents, Solvents and Glassware—
All solvents employed were obtained from Burdick and Jackson (Muskegan,
MI) and were redistilled prior to use. Chemicals used as standard reference
37
-------
materials were analytical reagent grade. Glassware was washed in
non-detergent soap, rinsed with deionized water, dried and then heated to
450°C in an oven for 2 h.
Air Samples—
Unexposed Tenax GC cartridges served as blanks from each batch prepared
for air sampling. The compounds listed in Table 13 were loaded onto Tenax
cartridges and served as controls for instrument calibration (1). Twenty-
three Priority Pollutants were loaded onto standard cartridges via a flash
tube evaporation system at 247°C as monitored by a thermocouple readout.
Samples were loaded via a 2 pL methanol injection into cryogenically scrub-
bed helium at a flow of 50 mL/min for 24 min. These cartridges served as
standards for the ambient air sample analysis. Blanks and controls were
analyzed along with samples.
Purgeable Organics from Liquid Samples—
Deionized-distilled water (prepurged) was spiked with the Priority
Pollutants listed in Table 13. The same compounds were added to 960 ml of
purged distilled water using methanol as the solvent. A minimum of 2 h was
allowed for equilibration. These samples were then employed as a source of
purge controls and no aliquot was employed 5 h after the preparation of this
solution. Unexposed Tenax cartridges served as blanks. Blanks and controls
were analyzed along with samples. Recoveries for water controls are given
in Table 13.
Instrumental Analysis
Priority Pollutants purged from liquid samples and cartridges used to
collect Priority Pollutants from the airstream were analyzed according to
previously described methods (1).
RESULTS AND DISCUSSION
The Priority Pollutant levels in the airstreams from an aeration tank
at the Northside Treatment Plant in Durham, NC are given in Table 14. Also
the levels for the same Priority Pollutants measured in the activated
sludge from aeration tank No. 2 are provided. Comparison of the air levels
of Priority Pollutants at locations 1 and 3 (representing the entrance and
exit of liquid flow for the aeration tank) indicates lower levels of Priority
Pollutants at the exit. For the most part, a decrease by a factor of 2 to 3
38
-------
Table 13. RECOVERY OF PRIORITY POLLUTANTS USED IN QUALITY CONTROL
to
VO
Compound
bis(2-chloroethyl)ether
1,1,1-trichloroe thane
1 , 2-dichloropropane
toluene
ethylbenzene
1, 1-dichloroethane
bromodichloroethane
brotnoform
chlorobenzene
chloroforn
ethylene dichloride
tetrachloroethylene
1 , 1 , 2, 2- tetrachloroethane
1,3-dichlorobenzene
acrylonitrile
trichloroethylene
carbon tetrachloride
benzene
trans- 1 , 2-dichloroethylene
methylene chloride
1,1, 2-trichloroe thane
1 , 2-dichlorobenzene
acrolein
Quantity added to
air sampling cartridges
(ng)
244
268
231
260
260
235
297
289
221
224
251
243
238
258
242
219
239
262
251
265
287
261
252
Quantity added to
10 ml "purged" waters
(ng)
254
279
241
270
270
245
308
300
345
310
262
337
327
268
252
304
331
272
262
275
300
270
265
Control No. 1
NDa
78
83+8
82 +_ 14
56 +_ 1
-
82+1
42 +_ 2
58 +_ 14
85+1
85 +_ 22
35 + 4
82 ^ 14
51
ND
59
65
73 ^ 6
111 + 4
39 + 2
57 +_ 4
-
% Recovery
Control No. 2
ND
87
99
86
-
-
116
-
76
115
-
69
-
72
ND
102
65
-
-
-
-
-
Control No. 3
-
107 +_ 3
75 +_ 12
68 +_ 7
-
100 +_ I
67 +_ 12
-
-
83 + 6
-
-
-
-
-
55 +_ 7
49+3
65 +_ 4
84 +_ 3
-
-
-
= not detected, - = not measured, values where indicated are mean + S.D. for triplicate
determinations, background subtract for "blanks". ~~
-------
Table 14. PRIORITY POLLUTANT LEVELS IN AIRSTREAMS AND
ACTIVATED SLUDGE FROM AERATION TANK NO. 2: PILOT STUDY -
NORTHSIDE TREATMENT PLANT, DURHAM, NC
(August 19, 1979)
Air3
Priority Pollutant LI L3 Sludge
Methylene chloride 53.1+8.5 37.7+4.3 32.4+12.4
Trichlorofluoromethane 21.4+4.8 6.3+0.6 3.6+1.8
1,1-Dichloroethylene 3.4+1.4 5.4+0.3 T
Chloroform 521.4+172.6 129.7+28.9 1.2+1.2
1,1,1-Trichloroethane 25.5 + 3.3 5.4 + 1.3 2.1 + 0.6
Carbon tetrachloride ND ND ND
Bromodichloromethane 15+3.4 8.4+1.6 ND
Trichloroethylene 49.6+5.9 22.8+5.0 5.8+1.4
Benzene 87.6+28.5 24.8+0.6 7.6+1.7
Tetrachloroethylene 463.2+27.9 109.3+8.8 2.5+0.1
1,1,2,2-Tetrachloroethane T ND T
Toluene 680.3 + 3.9 24.2 + 1.0 13.6 + 2.0
Chlorobenzene 8.9+1.5 3.4+1.3 0.7+0.7
Ethylbenzene 94.3+7.9 15.7+5.4 1.2+0.4
Dichlorobenzene isomer 287.1 + 12.9 133.1 + 12.1 5.6 + 1.5
aMean values are in ppb with standard deviation for triplicate samples.
Average values are in ppb with variation for duplicate samples.
T = trace, ND = not detected.
40
-------
was observed. The concentration in the activated sludge at the entrance
of aeration tank No. 2 is also indicated in Table 14. The concentrations of
the Priority Pollutants in the off-gas represent an integration over a
period of 4.5 h while the average concentration in the sludge is for a grab
sample at the beginning and end of each sampling period. In this Pilot
Study no inference can be drawn regarding the relationship between the
concentrations of the Priority Pollutants in sludge and in the off-gas from
the aeration basin.
Table 15 provides a comparison of the Priority Pollutant levels in
activated sludge at two different time periods in five aeration tanks. The
mean value, standard deviation and coefficient of variation were calculated
for each of the Priority Pollutants that were in measurable quantities.
Examination of the coefficients of variation indicates that a considerable
variation occurs between the aeration tanks despite the fact that samples
were collected at the same location, i-e., at the flow entrance into each
aeration tank. This variation suggests that obtaining precise measurements
of Priority Pollutant concentrations is difficult in activated sludge.
Whether this problem resides with the analytical methodology or is reflective
of the large variations in the input levels from one aeration tank to another
is unknown. Nevertheless, the Priority Pollutant levels in activated sludge
varied as much as 60% between the beginning and end of sampling of off-gas
from the aeration tank.
Table 16 presents the Priority Pollutant levels in raw wastewater in
the first experiment performed at the Northside Treatment Plant in Durham,
NC. The Priority Pollutants were determined at several different times
during a concurrent sampling of the off-gas from the aeration tanks. Fourteen
of the 34 volatile Priority Pollutants were detected in the raw wastewater
samples. Examination of the raw wastewater samples taken at various times
indicated that the Priority Pollutant levels varied up to a factor of 3 over
the 4.5 h period of the experiment.
Table 17 presents the Priority Pollutant levels in airstreams and
activated sludge from aeration tank No. 2 also for experiment No. 1. Results
for air levels are presented for two different time intervals and three
locations (entrance, middle, exit) and for levels in sludge at the beginning
41
-------
Table 15. COMPARISON OF PRIORITY POLLUTANT LEVELS IN ACTIVATED SLUDGE AT TWO DIFFERENT
TIME PERIODS: NORTHSIDE TREATMENT PLANT, DURHAM, NC - PILOT STUDY
Priority Pollutant
Methylene chloride
Trichlorofluoromethane
1,1-Dichloroethxlene
Chloroform
1,1, 1-Tr ich loroethane
Carbon tetrachloride
Bromodichloronethane
Trichloroethylene
Benzene
Tetrachloroethylene
1,1, 2, 2-Tetrach loroethane
Toluene
Chlorobenzene
Ethylbenzene
Dichlorobenzene
ATI3
21. 8b
1.7
Tc
2.0
1.1
ND
ND
S.I
7.3
2.0
ND
12.7
2.1
1.3
5.5
AT2
44.7
5.5
T
2.3
1.5
ND
ND
7.2
9.3
2.6
T
15.6
1.4
1.6
4.1
T = 0 h
AT4
11.7
1.8
NDd
2.4
0.9
ND
ND
5.2
7.1
1.7
ND
8.9
ND
ND
5.9
AT6
21.4
1.3
ND
1.9
ND
ND
ND
-
-
1.3
ND
7.3
1.3
1.0
3.9
ATS
30.3
1.7
ND
1.8
0.8
ND
ND
4.3
7.0
1.3
ND
15.5
1.2
1.4
4.1
ATI
44.6
6.2
ND
3.4
2.8
ND
ND
5.7
8.7
2.9
ND
12.6
1.7
1.3
7.5
T
AT2
20.0
1.8
ND
ND
2.7
ND
ND
4.5
5.9
2.5
ND
U.6
T
0.8
7.1
= 4 h
AT4
46.8
3.0
ND
3.7
2.7
ND
ND
4.5
9.2
2.9
ND
2.6
1.3
T
7.1
AT6
46.4
3.0
ND
3.5
2.4
ND
ND
2.4
8.2
2.0
ND
1.6
1.3
1.3
5.7
ATS
35.6
3.0
ND
2.4
5.7
ND
ND
4.5
10.5
2.0
ND
1.6
1.3
T
7.1
Mean +_ S.D. CC.V.)
32.3 +_ 13 (40)
2.9 + 1.7 (58)
T
2.3 +_ 1.1 (47)
1.9 + 1.2 (61)
ND
ND
4.3 +_ 1.9 (45)
7.3 + 2.9 (40)
2.1 + 0.6 (28)
T
9.0 + 5.5 (61)
1.3 +_ 0.5 (41)
1.1 *_ 0.5 (40)
5.8 *_ 1.4 (24)
ATI = aeration tank, No. 1, etc., see Fig. 2 , samples taken at entrance.
Values are in ppb.
CT = trace.
= not detected.
-------
Table 16. PRIORITY POLLUTANT LEVELS IN RAW WASTEWATER: NORTHSIDE TREATMENT PLANT, DURHAM, NC
EXPERIMENT NO. 1 (JANUARY 29, 1980)
CO
Sampling Time (h)
Priority Pollutant
Chlorome thane
Dichlorodifluoromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Trichlorof luorome thane
1 , 1-Dichloroethylene
1 , 1-Dichloroethane
trans-1 ,2-Dichloroethylene
Chloroform
1,2-Dichloroethane
1,1, 1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
Bis(2-chloroethyl)ether
1 , 2-Dichloropropane
trans-1 ,2-Dichloropropene
Trichloroethylene
1305
Ta
ND
ND
ND
ND
NC
ND
ND
T
ND
8.5 + 1.10
T
1.8 + 0.30
ND
T
ND
ND
ND
0.6 + 0.10
1400
0.8 + 0.05
ND
ND
ND
ND
NC
ND
ND
ND
ND
6.1 + 1.40
2.5 + 1.00
1.5 + 0
T
ND
ND
ND
ND
0.4 + 0.20
1525
0.7 + 0.30
ND
ND
ND
ND
NC
ND
ND
ND
ND
6.8 + 0.5
ND
2.0 + 0.70
ND
ND
ND
ND
ND
0.4 + 0.05
1615
T
ND
ND
ND
ND
NC
ND
ND
ND
ND
7.2
5.8 + 1.00
1.6
T
ND
ND
ND
ND
0.5 + 0
1740
T
ND
ND
ND
ND
NC
ND
ND
T
ND
10.8
ND
9.1
T
ND
ND
ND
ND
0.7 + 0
(continued)
-------
Table 16 (cont'd.)
Sampling Time (h)
Priority Pollutant
Dibromochloromethane
cis-1 , 3-Dichloropropene
1,1, 2-Trichloroethane
Benzene
2-Chloroethyl vinyl ether
Bromoform
1,1,2 , 2-Tetrachloroethylene
1,1,2 , 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Acrolein
Acrylonitrile
o-Dichlorobenzene
m-Dichlorobenzene
1305
ND
ND
ND
2.2 + 0.20
ND
ND
5.1 + 0.60
ND
11.7 + 1.50
ND
1.7 + 0.50
ND
T
0.8 + 0.20
2.2 + 0.10
1400
ND
ND
ND
2.5 + 0.50
ND
ND
2.6 + 0.40
ND
6.7 + 2.30
T
0.9 + 0.20
8.9 + 0.40
ND
0.5 + 0.05
1.8 + 0.30
1525
ND
ND
ND
2.4 + 0.10
ND
ND
3.5 + 0.40
ND
8.8 + 0.50
ND
0.8 + 0.10
6.5 + 0.70
ND
0.5 + 0.05
2.3 + 0.05
1615
ND
ND
ND
3.0 + 0.60
ND
ND
5.5 + 0.70
ND
20.1 + 3.90
ND
1.7 + 0.10
T
ND
0.5 + 0
1.6 + 0
1740
ND
ND
ND
3.8
ND
ND
4.7
ND
26.2
ND
2.1 + 0
T
T
0.8 + 0
2.5 + 0
.60
.10
.30
T = trace, ND = not detected, NC = not calculated. Values are in ppb.
-------
Table 17. PRIORITY POLLUTANT LEVELS IN AIRSTREAMS AND ACTIVATED SLUDGE FROM AERATION TANK NO. 2:
NORTHSIDE TREATMENT PLANT, DURHAM, NC - EXPERIMENT NO. 1 (JANUARY 29, 1980)
tn
LI
1200-1415 h
Priority Pollutant
Chloromethane
Di ch lorodif luoromethane
Bromoethane
Vinyl chloride
Chloroe thane
Methylene chloride
1.1-Dichloroethylene
1 , 1 - Di ch loroethane
trans- 1,2-Dichloroethylene
Chloroform
1 , 2-Dichloroethane
1,1. 1-Trichloroethane
Carbon tetrachloride
Bromodi Chloromethane
Bis(2-chloroethyl)ether
1,2-Dichloropropane
trans - 1 , 2-Dich loropropene
Trichloroethylene
Dibromoch lorometh ane
cis- 1 , 3- Dich loropropene
1,1, 2-Trichloroethane
Benzene
Air
NDC
ND
ND
ND
ND
14.6 (4.9)
ND
2.3 (5.4)
1.4 (2.7)
54.9 (6.1)
1.5 (8.1)
17.8 (3.3)
T
2.4 (0.7)
ND
ND
ND
9.1 (1.9)
ND
ND
ND
14 (6)
Sludge3
0.4 (0.02)
ND
ND
ND
ND
NC
ND
ND
ND
1.3 (0.3)
ND
0.9 (0.01)
0.2 (0.02)
ND
ND
NO
ND
0.2 (0.02)
ND
ND
ND
3.5 (0.80)
1415-1630 h
Air
ND
ND
ND
ND
ND
T
ND
1.5 (2.7)
ND
30.6 (1.2)
T
8.4 (1.6)
T
7.9 (0.9)
ND
ND
ND
5.7 (4.0)
ND
ND
T
3.3 (7)
Sludgeb
0.5 (0.05)
ND
ND
ND
ND
NC
ND
ND
ND
2.3 (0.4)
ND
1.9 (0.10)
1.4 (0.02)
ND
ND
ND
ND
T
ND
ND
ND
3.2 (0.60)
L2
1222-1435 h
Air
ND
ND
ND
ND
ND
34.6 (13)
ND
1.5 (2.4)
ND
42.9 (10)
2.2 (6.6)
11.8 (8.7)
T
8.1 (0.4)
ND
ND
ND
5.7 (4.0)
ND
ND
ND
3.8 (6)
1440-1650 h
Air
ND
ND
ND
ND
ND
T
ND
T
ND
56.7 (6.5)
T
12.7 (0.8)
T
8.0 (3.7)
ND
ND
ND
4.7 (0.5)
ND
ND
ND
3.9 (9.7)
L3
1240-1455 h
Air
ND
ND
ND
ND
ND
38.9 (8.3)
ND
ND
ND
23.9 (9.2)
ND
3.5 (8.5)
T
T
ND
ND
ND
2.2 (4.5)
ND
ND
ND
2.2 (15)
Sludge3
0.3 (0)
ND
ND
ND
ND
NC
ND
0.1 (0)
ND
3.1 (1.00)
T
1.3 (0.17)
ND
ND
ND
ND
ND
T
ND
ND
ND
1.9 (0.30)
1455-1705 h
Air
ND
ND
ND
ND
ND
40.9 (4.3)
ND
ND
ND
30.4 (1.6)
ND
3.8 (2.5)
T
5.4 (2.6)
ND
ND
ND
2.9 (2.1)
ND
ND
ND
2.4 (6)
Sludgeb
0.7 (0.02)
ND
ND
ND
ND
NC
ND
T
ND
3.7 (1.10)
T
1.3 (0.08)
ND
ND
ND
ND
ND
T
ND
ND
ND
1.5 (0.02)
(continued)
-------
Table 17 (cont'd.)
LI
1200-1415 h
Priority Pollutant
2-Chlorovinyl vinyl ether
Bronoform
1,1,2, 2-Tetrachloroethy-
lene
1,1 , 2, 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Aero le in
Acrylonitrile
o-Dl Chlorobenzene
m-Dichlorobenzene
Air
ND
NO
72.3 (2.7)
ND
95.3 (5.0)
ND
ND
ND
ND
9.0 (0.3)
30.5 (0.6)
Sludge3
ND
ND
1.1 (0.10)
ND
11.3 (1.60)
ND
0.4 (0.05)
10.2 (1.6)
ND
0.3 (0.03)
0.6 (0.06)
12
1415-1630 h
Air
ND
ND
26.4 (3.0)
3.0 (4.2)
5.5 (5.50)
T
1.8 (6.1)
ND
ND
7.7 (2.6)
27.6
Sludge5
ND
ND
1.5 (0.43)
ND
9.4 (0.10)
ND
0.4 (0.02)
4.6 (0.02)
ND
0.4 (0.05)
0.8 (0.20)
1222-1435 h
Air
ND
ND
25.1 (2.4)
T
5.8 (4.50)
T
1.6 (7.04)
ND
ND
7.4 (2.9)
26.6 (1,0)
1440-1650 h
Air
ND
ND
62.8 (5.4)
ND
4.3 (0.1)
1.6 (0.4)
2.9 (5.9)
ND
ND
7.9 (5.5)
39.0 (6.0)
1240-1455 h
Air
ND
ND
16.4 (2.3)
T
4.5 (4.5)
ND
ND
ND
ND
3.9 (3.9)
18.9 (1.5)
Sludge3
ND
ND
0.4 (0.05)
ND
9.1 (0.80)
ND
0.4 (0.02)
8.0 (1.35)
2.3 (0.35)
0.2 (0.0)
0.8 (0.01)
L3
1455-1705 h
Air
ND
ND
20.9 (3.0)
T
T
ND
ND
ND
ND
4.0 (0.6)
21.3 (0.8)
Sludge
ND
ND
0.8. (0.20)
ND
10.8 (1.47)
ND
0.3 (0.03)
7.1 (1.50)
1.0 (0.10)
0.1 (0.0)
0.8 (0.08)
Priority Pollutants were measured in sludge at the beginning and end of time period.
Priority Pollutants were measured at the beginning, middle and end of time period.
£
ND = not detected, T = trace, mean values are in ppb with coefficient of variation in parenthesis.
-------
and end of each air sampling period at two locations in the sludge. In
general, a decrease in the Priority Pollutant levels was observed in the
airstreams between locations 1, 2 and 3, respectively. However, the Priority
Pollutant levels in the activated sludge at locations 1 and 3 in the tank
for either of the sampling periods do not decrease. The reason for the
absence of a gradient in sludge between the front and end of the tank is not
clearly understood. Since it is possible that the Priority Pollutants are
distributed between the solid and liquid phases (as shown by the sorption
data in Table 7) the concentration which is measured for the liquid sample
appears to be relatively constant. This observation may be misleading. A
plausible explanation may be that the Bellar and Lichtenberg method (a He
stripping method) for measuring "purgeable" Priority Pollutants in sludge is
more efficient in removing organics dissolved in water (liquid phase) and
adsorbed to solids than the areation process in an activated sludge tank.
Thus, the sorption of organics to solids is reversed and they are stripped
from the liquid medium.
Comparison of the Priority Pollutant levels in raw wastewater with
activated sludge reveals significantly higher levels are generally found in
the raw sewage. Thus, vaporization of Priority Pollutants to the atmosphere
probably has occurred in other parts of the treatment facility (e.g., at
roughing filters, vacuators, etc.) prior to reaching the aeration basins.
A second experiment was conducted at the Northside Treatment Plant in
Durham, NC. Again Priority Pollutant levels were measured in airstreams and
activated sludge. In this case the experiment was performed at aeration
tank No. 4 on May 14, 1980. These results are given in Table 18. A compari-
son of the levels of the Priority Pollutants for this experiment with the
the pilot study and experiment No. 1 indicates a considerable variation in
the Priority Pollutant levels in the off-gas from aeration tanks. Also
considerable differences are observed for concentrations in the activated
sludge.
The results in experiment No. 2 (Table 18) also show a decreasing level
of Priority Pollutants in the off-gas between the flow entrance (LI) and
exit (L3) through the aeration tank. Again, as in experiment No. 2 (Table
47
-------
Table 18. PRIORITY POLLUTANT LEVELS IN AIRSTREAMS AND ACTIVATED SLUDGE FROM AERATION TANK NO. 4:
NORTHSIDE TREATMENT PLANT, DURHAM, NC - EXPERIMENT NO. 2 (MAY 14, 1980)
00
Priority Pollutant
Chloromethane
Dichlorofluorome thane
Bromoethane
Vinyl chloride
Chloroethane
Methylene chloride
Trichlorofluoromethane
1,1-Dichloroethylene
1, 1-Dichloroethane
trans- 1,2-Dichloroethylene
Chloroform
1 , 2-Dich loroethane
1,1, 1-Trichloroe thane
Carbon tetrachloride
Bromodichlorome thane
Bis(2-chloroethyl)ether
1 , 2-Dichloropropane
trans- 1 , 2-Dichloropropene
Tri ch loroethy 1 ene
Dibromochloromethane
cis-l,3-Dichloropropane
1 , 1 ,2-Trichloroethane
LI
1200-1415 h
Air
NDb
NO
ND
ND
ND
27.7+6.3
ND
8.0+0.2
2.8+0.5
NO
125+47.7
1.1*0.1
27.6+7.4
ND
4.7+0.8
ND
ND
ND
10.7+0.4
ND
ND
ND
Sludge3
ND
ND
ND
ND
ND
18.5+7.8
ND
4.0+0.4
ND
ND
27.8+U.2
ND
1.4+0.3
0.2+0
ND
ND
ND
ND
0.4+0
ND
ND
ND
1415-1630 h
Air
ND
ND
N!)
ND
ND
23.7+2.0
ND
6.8+0.2
3.8+0.5
ND
108+13.8
T
34.0+4.4
T
3.4+0.1
ND
ND
ND
9.4+2.8
T
ND
T
Sludge
ND
ND
ND
ND
Nb
34.2+21.6
ND
3.9+0.8
ND
ND
16.7+5.8
0.2+0
1.2+0.1
0.3+0.1
ND
ND
ND
ND
0.6+0.1
ND
ND
ND
1215-
Air
ND
ND
ND
ND
ND
9.7+1.0
ND
T
T
ND
52.9+13.9
T
6.7+1.4
T
T
ND
ND
ND
3.1+0.6
T
ND
ND
!
1430 h
Sludge
ND
ND
ND
ND
ND
51.4+6.0
ND
2.8
ND
ND
10.9^1.0
ND
1.1+0.6
T
ND
ND
ND
ND
0.4+0.1
ND
ND
ND
1.2
L3
1430-1645 h
Air
ND
ND
ND
ND
ND
7.1+0.6
ND
ND
T
ND
26.5+2.9
ND
6.4+0.7
ND
2.1+J).l
ND
ND
ND
1.7+0.2
ND
ND
ND
Sludge
T
ND
ND
ND
ND
27.9+3.2
ND
ND
ND
ND
16.5+1.4
ND
1.9+0.3
ND
ND
ND
ND
ND
0.4+0.1
ND
ND
ND
1215-1430 h
Air
ND
ND
ND
ND
ND
12.3+3.
ND
3.7+^1.
ND
ND
T
ND
T
ND
ND
ND
ND
ND
4.4
ND
ND
ND
Sludge
ND
ND
ND
ND
ND
.7 79.5+29.0
ND
,1 2.3+2.3
ND
ND
11.2+11.2
ND
0.4+0
ND
ND
ND
ND
ND
0.4+0.1
ND
ND
ND
1430-1650
Air
ND
ND
ND
ND
ND
17.1+0.3
ND
ND
ND
ND
8.4+0.6
T
1.3+0.2
T
ND
ND
ND
ND
4.8+1.7
ND
ND
ND
Sludge
ND
ND
ND
ND
ND
72.9+23.6
ND
ND
ND
ND
ND
ND
0.4+0.3
ND
ND
ND
ND
ND
0.3+0
ND
ND
ND
(continued)
-------
Table 18 (cont'd.)
1200-1415 h
Priority Pollutant
Benzene
2-Chloroethyl vinyl ether
1 , 1 , 2, 2-Tetrachloroethylene
Bromoform
1,1,2, 2-Tetrach loroe thane
Toluene
Chlorobenzene
Ethylbenzene
Acrolein
Acrylonitrile
m-Dichlorobenzene
o-Dichlorobenzene
Air
21. 2+4. 2
ND
119+26.3
ND
ND
136+52.4
T
26.4+8.4
ND
ND
38.1+13.2
11.3+2.4
Sludge3
1.0+0.2
ND
4.3+0.7
ND
ND
3.1+1.1
ND
0.7+0.2
ND
ND
3.6+0.4
2.5+0.6
LI
1415-
Air
18.8+1.5
ND
281+20.4
ND
ND
130+15
T
23.4+6.6
ND
T
36.3+6.9
10.5+2.6
-1630 h
Sludge
1.1+0.1
ND
12.2+2.1
ND
ND
3.5+1.0
ND
0.4+0.4
ND
ND
3.9+1.2
2.5+0.8
1215-1430 h
Air
4.8+0.9
ND
32.1+9.8
ND
ND
18.4+6.0
ND
9.1+1.4
ND
ND
31.6+7.4
10.2+2.7
Sludge
1.3+0.
ND
2.8+0.
ND
ND
21.4+20
ND
0.5+0.
ND
ND
3.0+1.
1.8+0.
12
1430-1645 h
Air
2 2.7+0.3
ND
4 40.9+4.4
ND
ND
.0 5.5+1.0
ND
1 4.3+0.5
ND
ND
4 14.0+1.6
4 3.9+0.6
Sludge
1.1+0.2
ND
3.8+0.8
ND
ND
1.9+0.3
ND
0.4+0.1
1.7+1.7
ND
3.6+1.4
2.1+0.5
1215-1430 h
Air
7.2
ND
3.1+0.1
ND
ND
27.1+5.5
ND
0.9+0
ND
ND
4.2+0.2
1.1+0
Sludge
1.2+0.3
ND
1.7+0.5
ND
ND
10.9+9.3
T
0.3+0.1
ND
ND
3.0+1.1
1.6+0.1
L3
1430-1650
Air
7.9+2.7
ND
6.0+1.1
ND
ND
8.1+0
ND
0.7+0.3
ND
ND
4.3+0.6
1.3+0.2
Sludge
0.9+0.3
ND
1.3+0.2
ND
ND
11.6+8.6
T
0.1+0.1
ND
ND
2.9+0.4
1.7+0.4
Priority Pollutants were measured in sludge at the beginning and end of time period
the mean value of quadruplicate analyses reported.
3ND = not detected, T = trace, mean values are in ppb with standard deviation.
with
-------
17), the concentrations of the Priority Pollutants in sludge were relatively
constant or slightly increased in some cases at each of the locations.
In order to estimate the emission rates from the entire composite
aeration tank area, it is necessary to have the following pieces of data:
(1) the off-gas volume flow per square foot of tank area; (2) the total
number of square feet for the composite tank area; and (3) the concentration
of the Priority Pollutant in the off-gas per unit time. The off-gas flow
rate per unit area can be obtained by one of two methods. The off-gas
volume may be obtained from the air injection rate recorded by the plant
(gas flow pumped through the diffusers in the aeration tanks). A second
method is to determine the off-gas flow rate per unit area with the Nutech
sampler. Since the total off -gas flow per square foot passes through and is
recorded by the gas meter on the sampler, it is thus possible to obtain a
total flow per unit time or period of sampling. An average off-gas rate can
be calculated.
Emission rates were calculated for selected Priority Pollutants and for
each study (Pilot and Expts. No. 1 and 2) to determine the extent of pollu-
tion associated with the aeration tanks at the Northside Treatment Plant in
Durham. An example calculation for chloroform (Pilot Study) is as follows:
o
(1) off-gas rate - 26.90 L/min/m
(2) total surface area of aeration tanks -
4.571 m x 61.0 m 0 . , ™0n ^ 2
- : - x 8 tanks = 2230.6 m
tank
(NOTE: only 8 of 9 tanks were operating)
(3) total off-gas volume/h -
3 3
26.9 L „„,,-. , 2 60 min 1 m _ 0 £.„ m
— : - 7 x 2230.6 m x — r - x , ..nr. T = 3,600 7—
mm • nr h 1000 L h
(4) mean chloroform level per tank -
325 PPb , 4.92 tt x x .
where 1 ppb = 4.92 jJ
L
50
-------
(5) emission rate -
1 *™ -n_ _ 5>756 4 g/h
Emission rates for all of the studies for each Priority Pollutant
measured are given in Table 19. The highest rates were observed for chloro-
form and 1,1,2,2-tetrachloroethylene with emissions reaching 5.7 kg/h and
7.0 kg/h, respectively, in the Pilot Study.
51
-------
Table 19. ESTIMATED EMISSION RATES CALCULATED FOR SELECTED PRIORITY POLLUTANTS FROM AERATION
BASINS AT NORTHSIDE TREATMENT PLANT, DURHAM, NC
Priority Pollutant
Methylene chloride
1 , 1-Dichloroethane
Chloroform
1 , 2-Dichloroethane
1 , 1 , 1-Trichloroethane
Bromodichloromethane
Trichloroethylene
Benzene
1,1,2 , 2-Tetrachloroethylene
Toluene
Ethylbenzene
o-Dichlorobenzene
m-Dichlorobenzene
August 19, 1979
572
-
5,756
-
301
288
704
668
7,007
4,819
871
14,689
Emission Rates (g/h)
January 29, 1980
280 + 86
14 + 4
703 + 11
10 + 7
191 + 27
130 + 42
103 + 11
62 + 9
940 + 15
264 + 216
16 + 8
148 + 3
609 + 44
May 14, 1980
205 + 3
19 + 2
944 + 103
5 + 2
252 + 23
43 + 1
111 + 8
122 + 8
1,969 + 710
741 + 86
171 + 21
478 + 71
155 + 13
-------
SECTION 7
IDENTIFICATION OF CHLORINATED COMPOUNDS IN SLUDGE FROM A
SUPERCHLORINATION PROCESS
INTRODUCTION
Sampling and analysis for chlorinated compounds which might be produced
by the stabilization of sludge via a superchlorination process were conducted.
The objective of this study was to determine whether any chlorinated organics
were present in the fraction which is amenable to gas chromatography since
reports indicate 1 to 3% chlorine was associated with the organics (3,4).
Sampling and analysis was conducted for qualitative characterization of
chlorinated organics using electron impact and negative ion chemical ioniza-
tion capillary gas chromatography/mass spectrometry (GC/NICIMS).
EXPERIMENTAL
Plant Characteristics
Two plants were sampled. The first was located in Rocky Mount, NC.
The sewage treatment plant of Rocky Mount operates with an average flow of
41.64 mid (^50% industrial) and an average chlorination dose of 800 to 900
mg chlorine per liter of sludge influent, and an average time of 24 h in
settling beds. Figure 6 depicts a schematic of the superchlorination process
and the locations where samples were obtained. The second plant was located
in Fayetteville, NC, and operated under similar conditions.
Sampling
Grab samples of digested influent and chlorinated effluent were taken
in duplicate at three 1 h intervals from access valves (Fig. 6). A glass
funnel washed after each sample duplicate was used to direct the pressurized
®
flow into 1 L amber bottles which were sealed with Teflon -lined caps.
Semisolid samples from the settling beds (Fig. 7 and 8) were scooped with a
1 L beaker and transferred via a glass funnel to 1 L glass amber bottles
®
with Teflon -lined caps. Cake sludge from the settling beds was transferred
53
-------
PROCESS PRESSURE
VENT
,
1
RECIRCULATION
LOOP
0
J
v_x-
IMW
"^*""*'"^-^.
T '
Bfit-vj
(EQUIPMENT WITHIN THE
PURIFAX CHEMICAL OXIDIZER
Vent Mo. 2
OUTLET
(PROCESSED MATERIAL)
PRESSURE
CONTROL
LVJIH i nui. |
PUMP |
I 13 I CHLORINATOR
J
PRESSURE SWITCH
VACUUM SWITCH
PRESSURE AND/OR VACUUM GAUGE
MACERATOfl
FEEDPUMP
FLOW METER
FLOW METER RECEIVER (WITH
ADJUSTABLE CONTACTS)
FEEDPUMP
RECIRCULATION PUMP
FIRST REACTOR
SECOND REACTOR
PRESSURE CONTROL PUMP
MOTOR STARTER PANEL
EDUCTOR
VACUUM LINE VALVE (ELECTRIC)
M2) DIAPHRAGM CHECK VALVE
© CHLORINATOR
@ CHLORINE PRESSURE REDUCING &
SHUT-OFF VALVE
CONTROL PANEL
6) ALARM BELL
SOLENOID VALVE
PRESSURE REGULATOR
(19) LIQUID CHLORINE EVAPORATOR
CHLORINE
PRESSURE
POWER (ON-OFF)
START PUSHBUTTON. GREEN LIGHT (RUN)
RED LIGHT (LOW VACUUM)
RED LIGHT (LOW CHLORINE PRESSURE)
CHLORINE VALVE (OPEN-CLOSE-AUTOI
STOP PUSHBUTTON
RED LIGHT (LOW PLOW)
00 RED LIGHT (MACERATOR OVERLOAD!
(T) AUDIBLE ALARM (ON-OFF)
(j) EMERGENCY STOP - RESET PUSHBUTTON
(K) ALARM RESET PUSHBUTTON
(T) RED LIGHT (OVER PRESSURE)
(M) RECIRCULATION PUMP IHAND-OFF-AUTOI
(N) PRESSURE CONTROL PUMP (HANO-OFF-AUTO)
PFX-C-39
Figure 6. Schematic of Superchlorination Process at Rocky Mount and Fayetteville, NC and locations
of sampling (Vent No. 1 - Influent, Vent No. 2 - Effluent).
-------
Superchlori-
nation
Process
Figure 7. Sampling locations (asterisks) for settling beds
(Nos. 1-10) at the Rocky Mount, NC site.
55
-------
•x.601
Grab Sample
Barrier
Metal bar
Chlorinated sludge flow
Figure 8. Chlorinated sludge entering settling bed at Fayetteville
Municipal Wastewater Treatment Facility exhibiting where
sample was taken.
56
-------
to wide-mouth quart jars wrapped with an aluminum foil and sealed with
Teflon -lined caps. The sampling protocols for the superchlorination proces-
ses at Rocky Mount and Fayetteville, NC are given in Tables 20 and 21.
Chlorine Determination in Samples from Fayetteville Treatment Plant
The total chlorine of each sample was fractionated into the free chloride
ion of the supernatant, the organic chlorine content of finely suspended
solids and aqueous soluble organics, and the organic chlorine content of
insoluble particulates. The latter two fractions necessitate a Schoniger
oxidation and collection of water soluble gases prior to analysis (5).
Potentiometric titration of chloride ion with standard silver nitrate
using a solid state silver chloride/saturated calomel electrode was the
method used. A linear response to chloride ion was established over approxi-
mately four orders of magnitude, and a single titration of sodium chloride
in deionized water yielded an accuracy of 1.8% relative standard deviation.
The Schoniger method was used for the determination of organic chlorine
(5). Seventy-five grams of each sludge was centrifuged (^2000 rpm) until a
tightly packed solid was achieved. Supernatant volumes were determined in a
®
graduated cylinder and then refrigerated in glass amber bottles with Teflon -
lined caps. The solids were resuspended in deionized water, centrifuged and
the solids transferred to previously tared crucibles or watch glasses.
Residual liquid was allowed to evaporate at ambient temperature for a period
of 3 days.
Combustion of 25 to 35 g of each air-dried solid sample was conducted
in a 500 ml Schoniger oxidation flask according to the method of Welcher and
Ma (5). The flask was allowed to stand a minimum of 1 h after combustion.
Samples not immediately analyzed were refrigerated.
The method of standard addition was used with standard sodium chloride
to generate regression curves for all supernatant and combusted solids. A
minimum of 3 data points was employed for each regression.
Combustion products were acidified with nitric acid and titrated with
no dilution. Influent samples also required no dilution. Effluent samples
required a 1:100 dilution to achieve an approximately 0.035 g/L concentration
to be within the linear response region of the ion specific electrode.
57
-------
Table 20. SAMPLING PROTOCOL FOR SUPERCHLORINATION PROCESS AT WASTEWATER TREATMENT PLANT
IN ROCKY MOUNT, NCa
Ln
CO
Sample
RINF
RINF
RINF
RINF
RINF
RINF
REFF
REFF
REFF
REFF
REFF
REFF
RBED
RBED
RBED
RBED
Code
1S1
1S2
2S1
2S2
3S1
3S2
1S1
1S2
2S2
2S1
3S1
3S2
SI
S2
S3
S4
Sample Type
influent sludge
influent sludge
influent sludge
influent sludge
influent sludge
influent sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
14 day-old chlorinated sludge from settling bed
4 day-old chlorinated sludge from settling bed
1 day-old chlorinated sludge from settling bed
2 hour-old chlorinated sludge from settling bed
Sampling Time
12:30-12:40
12:30-12:40
13:25-13:35
13:25-13:35
14:30-14:40
14:30-14:40
12:30-12:40
12:30-12:40
12:30-12:40
13:25-13:35
14:30-14:40
14:30-14:40
-
-
-
13:45
Samples were acquired on June 6, 1979.
-------
Table 21. SAMPLING PROTOCOL FOR SUPERCHLORINATION PROCESS
AT WASTEWATER TREATMENT FACILITY IN
FAYETTEVILLE, NCa
Sample Code
FINF 1S1
FINF 1S2
FINF 2S1
FINF 2S2
FINF 3S1
FINF 3S2
FEFF 1S1
FEFF 1S2
FEFF 2P1
FEFF 2P2
FEFF 3S1
FEFF 3S2
FEED SI
FEED S2
Sample Type
influent sludge
influent, sludge
influent sludge
influent sludge
influent sludge
influent sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
effluent chlorinated sludge
chlorinated sludge from settling bed
chlorinated sludge from settling bed
Sampling Time
11:10-11:15 AM
11:10-11:15 AM
12:10-12:12 PM
12:10-12:12 PM
1:11-1:16 PM
1:11-1:16 PM
11:10-11:15 AM
11:10-11:15 AM
12:10-12:12 PM
12:10-12:12 PM
1:11-1:16 PM
1:11-1:16 PM
1:00-1:05 PM
1:00-1:05 PM
Samples acquired on September 19, 1979.
59
-------
Twenty to twenty-five ml of influent sludge or chlorinated effluent sludge
was titrated.
Standard sodium chloride solution was added to the sample after each
endpoint was determined until the change in potential was maximum. Standard
sodium chloride solution was initially added to influent samples but not to
effluent samples. The liquid sample was vigorously stirred and was shielded
from light. Standard silver nitrate solution was added using a buret accurate
to +0.02 mL.
Single endpoint analyses of a standard sodium chloride solution and
combusted p_-chlorophenoxyacetic acid were conducted. The former yielded a
percent relative standard deviation of 1.8%; the latter 5.7%. The increased
variability was attributed to the combustion step in this procedure.
Sample Purification
Volatiles--
A modification of the EPA Interim Protocol "V100 - Methods for Purgeable
Organics" was utilized (6). A sludge volume equivalent to 50 mg dry solids
determined by evaporation and weighing of four 2 ml homogeneous aliquots was
added to sufficient deionized water (previously purged with helium at 40
mL/min for 16 min) in a 10 ml Bellar apparatus to give a final volume of 10
mL. The Bellar apparatus was then capped with a 1.5 cm x 6.0 cm Tenax GC
sorbent cartridge and its contents were purged for 12 min with helium at 40
®
mL/min. The cartridge was then transferred to a foil wrapped Kimax culture
tube containing calcium sulfate previously baked for 4 h at 400°C, sealed
with Teflon -lined caps and then analyzed by GC/MS.
Semivolatiles—
The EPA Interim Protocol"B100 Method for Semivolatile Organic Components"
was followed with minor modifications (7).
Extraction--
Solvent and blanks from the extraction procedure for both acid/neutrals
and bases were processed according to the protocol.
Acids and Neutrals—Four 25 g aliquots of representative liquid sludge
®
were transferred to 50 mL centrifuge tubes with Teflon -lined caps and acidi-
fied with 1.45 g of hydrated potassium bisulfate. Each tube was extracted
three times with 25 mL of distilled methylene chloride for 5 min on a shaker
60
-------
and then centrifuged. The combined methylene chloride extracts were filtered
through glass wool into receiving flasks. Extracts were dried over sodium
sulfate which had been previously extracted with pentane.
Bases—Five g of thoroughly mixed liquid sludge was buffered with 10 mL
®
of 0.1N H-PO./HPO, in a 50 mL centrifuge tube sealed with a Teflon -lined
cap and twice extracted with CH-Cl- followed by centrifugation with 5 mL of
redistilled chloroform. The combined solvent extracts were dried over
sodium sulfate. Extracts were twice extracted with 2N sulfuric acid solutions
®
for 5 min in culture tubes equipped with Teflon -lined caps. Aqueous extracts
were neutralized by addition of 1.0 mL of 0.4N sodium phosphate and dropwise
addition of 20% ammonium hydroxide. The organics were partitioned into two
10 mL chloroform extracts which were then washed with 5 mL of distilled
water, dried over sodium sulfate, concentrated in a Kuderna-Danish (K-D)
apparatus to 0.4 mL, gently blown down to 0.2 mL under ambient nitrogen, and
then analyzed by GC/MS.
Acid and Neutrals—Methylene chloride extracts were concentrated to ~70
mL, partitioned with 200 mL of petroleum ether (Burdick and Jackson) using
three successive 400 mL portions of 0.1N sodium hydroxide/10% sodium chlo-
ride in a 1 L separatory funnel, then twice with 200 mL 10% sodium chloride.
The organic layer was dried over sodium sulfate. The fraction was then
concentrated to <200 mg/mL of soluble organics for GPC analysis.
Preparation of Gel Permeation Chromatography--A 1.3 cm x 110 cm Chroma-
tronix column was packed with biobeads SX-8 previously swelled in methylene
chloride such that the required operating flow did not exceed 15 psi. An
FMI pulseless pump was adapted for upward flow and detection was achieved by
a UV photometer [(254 run) mercury ultraviolet lamp].
Standard solutions were used which established the GPC windows for
fractionation of the acid and neutral extracts previously prepared.
Calibration Solution—A methylene chloride solution containing approxi-
mately 45 |Jg/mL of corn oil and ~2 (Jg/mL of di-n-octyl phthalate, dimethyl
phthalate, |>-chlorophenyl phenyl ether, pyrene, and sulfur was employed to
establish windows for the neutral fractions from the GPC column. The compo-
nents eluted in the order described. Fraction 1 (NF1) of each extract was
collected as the minima between the corn oil/octyl phthalate and dimethyl
61
-------
phthalate/£-chlorophenyl phenyl ether sets. Fraction 2 (NF2) was collected
as the remaining elements up to the pyrene/sulfur minimum.
A methylene chloride solution containing approximately 2 Mg/mL each of
n-octanoic acid, 2,4-dimethylphenol, 2,4-dinitrophenol, and sulfur was
employed to establish windows for the acid fraction. The elution order was
as described. The acid fraction (ATI) was taken as the minima of the n-octa-
noic acid/dimethylphenol and the dinitrophenol/sulfur sets.
Operating Conditions--Two ml injections of both standards and samples
®
were made via a three way valve connecting a 10 ml glass jacket-Teflon
barrel syringe to the system pump and GPC column. Repeated calibrations
with continual monitoring and maintenance of degassed methylene chloride
flow at 1 mL/min indicated the existence of moderately reproducible windows
(1-2 min). Column efficiency was a function of a given calibration run and
varied from 850-1950 theoretical plates from one GPC column to another.
The previously extracted acids/neutral effluent and bed samples were
concentrated to ^2 ml in a micro K-D apparatus containing uncoated glass
capillary fragments to minimize bumping. Following calibration of the
system, a 2 mL aliquot of extract was directly injected onto the column.
Liquid fractions were collected in 250 mL centrifuge tubes previously
washed and oven dried.
Dry sample remaining in the syringe or transfer line to the three way
valve was diluted with methylene chloride to 2 mL and injected as a record
run. Sample remaining in the transfer line after this dilution was then
removed and disposed.
Workup of Extracts and GPC Fractions--
Neutrals in GPC Fraction—Fraction 1 (NF1) was concentrated to 2 mL,
diluted to 4 mL with petroleum ether and transferred to an 8 x 900 mm chroma-
®
tography column (with Teflon stopcock) packed with 20 g activated Grade 923
silica previously washed with 50 mL of 25% acetone/methylene chloride and 50
mL of petroleum ether. The fraction was eluted with 50 mL of 50% pet ether/
methylene chloride and 50 mL of 25% acetone/methylene chloride. The latter
fraction was combined with fraction 2 (NF2) from the GPC run and concen-
trated to ^-6 mL. The extract was then transferred to a micro K-D with vl mL
of ethylene dichloride. The fractions were then concentrated to ^500 |JL
62
-------
and 10 |Jg of d,--anthracene was added. Solvent exchange with tetrahydrofuran
was then necessary for GC/MS analysis.
Pre- and post-GPC column fractions and their corresponding blanks were
concentrated to approximately 500 |JL and then subjected to GC/MS analysis.
Preparation of the neutral window fraction for analysis requires
fractionation of the first of two collected fractions onto silica gel. An
eluant of an intermediate polarity (25% acetone in methylene chloride) was
collected with the disposal of a non-polar (50% pet. ether in methylene
chloride) fraction. The first window fraction of Effluent No. 1 was regenera-
ted with the retention of this non-polar eluant for analysis. The column
was then flushed with acetone to collect a polar fraction for GC/MS analysis.
The final solvents for the fractions were, respectively, THF and acetone.
Acids in GPC Fractions-^The GPC fractions were concentrated to approxi-
mately 3 ml and partitioned between 20 ml of hexane and 20 mL of 0.1N NaOH/10%
®
in a 50 mL culture tube equipped with a Teflon -lined cap. The partitioned
extracts were then oscillated on a floor shaker for 20 min, after which time
the basic fraction was isolated and the extraction repeated. The combined
basic fractions were acidified with 6N HC1 and twice partitioned into methy-
lene chloride. The organic extracts were dried over extracted sodium sulfate,
filtered into a K-D apparatus, concentrated to VJ mL, and transferred to a
micro K-D with approximately 1 mL of ethylene dichloride. Concentration was
continued to approximately 500 |JL and 10 |jg of d,--anthracene was added.
Solvent exchange with tetrahydrofuran was then performed.
In addition to the collection of acid and neutral fractions that eluted
from the gel permeation column within the previously established window,
fractions prior to and following these windows were also collected for GC/MS
analysis. All seven acid window fractions and one blank were prepared
according to the protocol.
One fraction of a neutral extraction was subjected to removal of polar
and non-polar interferences via silica gel chromatography. In the conven-
tional Priority Pollutant protocol, these fractions are normally discarded;
however, these fractions were kept for GC/MS analysis. Since the solvents
methylene chloride or ethylene dichloride are incompatible with analysis by
63
-------
negative ion chemical ionization, a solvent exchange was conducted of all
the extracts with the final solvent of choice being tetrahydrofuran.
The pre- and post-column fractions of influent and effluent numbers 2
and 3 and the corresponding blanks were concentrated to ^2 mL and subjected
to basic extraction and acidification per the protocol established for the
window acid fraction. The organic extracts were concentrated to approxima-
tely 300 to 400 mL and 100 |JL of N-methyl-N-trimethylsilyl trifluoroacetamide
(MSTFA) were added. The extracts were allowed to stand overnight at ambient
temperature to allow derivatization to occur. The window fraction of
sample effluent No. 1 was regenerated and silanized to observe any disparity
between silanized and unsilanized detection limits.
Analysis of the supernatant of Effluent No. 1 via the method of standard
addition yielded an excellent fit for a least squares analysis and an
extrapolated concentration of 0.143N in chloride ion. A repeat analysis
yielded 0.141N; thus, an average of 0.142N in Cl was observed.
Instrumental Analysis
The samples were analyzed on an LKB 2091 (PDF 11/04 Data System) gas
chromatograph/mass spectrometer/computer system utilizing both electron
impact and negative ion chemical ionization. The use of negative chemical
ionization was especially useful since it is highly selective and sensitive
to electron capturing compounds. Because many chlorinated compounds possess
a high electron capture coefficient, they would be particularly amenable to
negative ion chemical ionization. Tables 22 and 23 present the GC/MS condi-
tions for acid and other fractions, respectively. The neutral fractions
were chromatographed on a 25 m wall coated open tubular column (fused silica)
coated with SP-2100 phase. These fractions were also chromatographed on a
conventional 6 ft 1% SP-2250 coated packed column. The acid fractions were
analyzed on a 6 ft packed column containing 1% SP-1240 DA.
RESULTS AND DISCUSSION
Organic Chlorine Concentration
A study of the linearity of detection indicated that a wide scattering
for influent sludge titrations may result from interferences not encountered
in the highly diluted chlorinated effluent sludge samples. Negative and
positive intercepts of the abscissa were obtained with the application
64
-------
Table 22. GC/MS CONDITIONS FOR FAYETTEVILLE ACID FRACTIONS
Parameter
Ion source temperature
Electron energy
Trap/box current
Reagent gas
Reagent gas pressure
Positive ion
210°C
70 eV
50 yA
-
_
Negative ion
210°C
50 eV
250 yA
Methane
4 x 10"5 T
Accelerating voltage
Scan interval
Column
Temperature program
Helium flow
Injector temperature
-Separator temperature
3500 V
2.0 sec
1.82 m 1% SP1240 DA
85°C/1 min then
10°C/min to 200°C
14.0 mL/min
220°C
210°C
3500 V
2.5 sec
1.82 m 1% SP1240 DA
85°C/min then 10°C/
min to 200°C
14.0 mL/min
220°C
210°C
65
-------
Table 23. GC/MS CONDITIONS FOR OTHER FAYETTEVILLE FRACTIONS
Parameter
Ion source temperatur*
Electron energy
Trap/box current
Reagent gas
Reagent gas pressure
Accelerating voltage
Scan Interval
Column
Temperature program
Ox
ON
Helium flow
Injector temperature
Separator temperature
Positive Ion Negative Ion
250°C 250°C
70 eV 50 eV
50 uA 250 uA
Methane
4 x 10"5 T
3500 V 3500 T
2.0 sec 2.0 sec
25 M SP2100 WCOT (Hewlett-Packard) and 1.85 m l\ SP2250 25 M SP2100 WCOT and 1.85 • 1% SP2250
50°C for 4 mln then 8°/mln to 260°C 50°C/4 mln then 50°C/4 mln, 8°/mln 50°C/4 mln
for 20 mln 8*/mln to 260°C/ to 20 mln 8° /mln to
20 mln 260°C/20 mln
.73 mL/mln 14.0 mL/mln .73 mL/mln 14.0 mL/mln
220°C 250°C 220°C 250"C
250°C 275°C 250°C 275'C
-------
of linear regression to the influent data. Thus, an ultimate detection
limit was estimated.
The linear regressions for the influent sludge combustion products all
yielded positive abscissa intercepts and supported the proposition of inter-
ferences. The mean of these positive intercepts was taken as a chloride ion
equivalent detection limit. The value based upon these three samples was 6
+ 3 x 10 equivalents of chloride ion. The percentage of chloride ion
detection limit for the combusted solids based on these values was 0.6 + 3%
(% standard deviation).
The 20 mL of Schoniger adsorption solution after combustion approached
the 25 mL volume of supernatant titration. Thus, it was not unreasonable
to employ the solid limit of detection to establish the supernatant limit of
-3
detection. For a 25 mL sample, the numerical value was 8.3 + 1.2 x 10 g/L
of chloride ion.
Two of the three influent supernatants approached the abscissa asympto-
tically and indicated a greater chloride content than a linear regression.
_2
However, the greater of the two values, 2.45 x 10 g/L, is less than an
order of magnitude and may be taken as the upper limit of influent chloride
ion content.
The values presented in Table 24 may be the upper chloride ion concen-
trations limits since interfering species may also precipitate silver ion.
The results for the organic chlorine content for superchlorinated
sludges and supernatants obtained from the Fayetteville, NC plant are given
in Table 24.
Identification Measurement of Chlorinated Compounds
Rocky Mount (Pilot Study)--
Extracts of samples from the superchlorination process were analyzed by
GC/MS/COMP using electron impact and negative ion chemical ionization modes.
Table 25 presents the results for the purgeable chlorinated compounds
identified in an influent sludge and chlorinated effluent sludge from the
process.
Tables 26 through 29 lists the chlorinated substances which were identi-
fied in the extract fractions of the immediate effluent and sludge (from the
settling pond). Several chlorinated hydroxybenzene analogs were detected
67
-------
Table 24. ORGANIC CHLORINE CONTENT FOR FAYETTEVILLE, NC
SUPERCHLORINATED SLUDGES
Sample Code
FINF 1S1
FINF 2S2
FINF 3S2
FEFF 1S1
FEFF 2S2
FEFF 3S2
FEED SI
Supernatant
<7 x 10"4 Na
-L
<7 x 10 N
-4
<7 x 10 N
0.138N, 0.143N
0.132N
0.086N
0.107N
Solid
<0.6 + 0.3%
<0.6 + 0.3%
<0.6 + 0.3%
5 . 28%
2.15%, 2.28%
2.99%
4.50%
Expressed as equivalents of chloride ion.
68
-------
Table 25. "PURGEABLE" CHLORINATED COMPOUNDS IDENTIFIED IN
EFFLUENT FROM A SUPERCHLORINATION AT ROCKY MOUNT, NC FACILITY*
Chromato-
graphic
Peak No.
1
2
3
4
5
6
7
Elution
Temp.
CO
44
49
54
63
64
67
72
Compound
co2
chloroethane
nethylene chloride
hexaf luorobenzene (el)
chloroform
perf luorotoluene (eW)
carbon tetrachloride
Chromato-
graphic
Peak No.
8
9
10
11
12
Elution
Temp.
CO
78
101
107
138
168
Compound
trichloroethylene
tetrachloroethylene
chlorobenzene
dichlorobenzene isomer (trace)
trichlorobenzene isomer
(traces)
Sample taken at the immediate outlet from superchlorination process
(1230-1240 h, 6/6/79).
69
-------
Table 26. CHLORINATED COMPOUNDS IDENTIFIED IN THE NEUTRAL FRACTION
OF EFFLUENT FROM THE SUPERCHLORINATION AT
ROCKY MOUNT, NC FACILITY21
Peak No.
1
2
3
4
Elution Temperature
65
109
162
171
Compound
solvent
trichlorobenzene isomer
dichlorobenzoic acid isomer (tent.)
chlorinated compound (unknown)
Sample taken at immediate outlet from the superchlorination process
(1325-1335 h, 6/6/79).
70
-------
Table 27. CHLORINATED COMPOUNDS IDENTIFIED IN THE ACID FRACTION OF EFFLUENT FROM
THE SUPERCHLORINATION AT ROCKY MOUNT FACILITY3
Peak No.
1
2
3
4
5
Elution Temperature
161
162
178
199
200
Compound
dichlorocresol isomer
chloroamylphenol isomer (tent.)
alkyl chlorophenol isomer
chlorinated compound (unknown)
methylchlorohydroxybiphenyl isomer
(tent.)
«J
Sample taken at immediate outlet from the superchlorination process (1325-1335 h, 6/6/79)
-------
—J
Is?
Table 28. CHLORINATED COMPOUNDS IDENTIFIED IN THE NEUTRAL FRACTION OF SLUDGE FROM
SETTLING BED OF THE SUPERCHLORINATION AT ROCKY MOUNT, NC FACILITY3
Peak No.
1
2
3
4
5
6
7
Elution Temperature (°C)
60
60
122
160
177
177
185
Compound
1 , 2-dichloroethane
dichlorome thane
chlorinated compound (unknown, trace)
dichlorobenzoic acid isomer
chlorinated compound (unknown)
chlorinated compound (unknown)
chlorinated compound (unknown)
^Sample was taken from a 2 h old settling bed (1345 h, 6/6/79).
-------
CO
Table 29. CHLORINATED COMPOUNDS IDENTIFIED IN THE ACID FRACTION OF SLUDGE FROM SETTLING BED OF
THE SUPERCHLORINATION PROCESS AT ROCKY MOUNT, NC FACILITY&
Peak No.
1
2
3
4
5
6
7
8
9
Elution Temperature (°C)
121
134
160
161
169
178
184
197
200
Compound
2,3-Dichloropropanol-l (tent.)
6-Chloro-o-cresol or Methylchlorophenol isomer
4,6-Dichloro-o-cresol or Dichlorocresol isomer
C,. -Alkyl chlorophenol isomer (tent.)
Trichlorophenol isomer
Alkyl chlorophenol isomer
Alkyl chlorophenol isomer
Chloro compound (unknown)
Methylchlorohydroxybiphenyl isomer (tent.)
1
Sample was taken from a 2 h old settling bed (1345 h, 6/6/79).
-------
and further confirmed by negative ion chemical ionization GC/MS. However
the levels of these compounds were very low. Sample extracts which were
derivatized did not reveal new components.
Table 30 gives the measured levels of "purgeable" organics in the
sludge samples. Comparison of the levels of the selected purgeable organics
between the influent and chlorinated effluent sludges indicates that several
compounds increased appreciably. These compounds were chloroform, carbon
tetrachloride, and p_-chlorotoluene (Table 24). The concentrations of the
remaining organics which were measured in these samples did not appear to
increase in concentration after the superchlorination process.
Fayetteville, NC—
Table 31 lists the extracts and fractions generated during processing
of samples from the Fayetteville, NC site.
GC/MS/COMP utilizing both electron impact and negative chemical ioniza-
tion modes were employed for the analysis of fractions derived from the
samples taken at the Fayetteville, NC site. Figures Al through A106 (Appen-
dix A) present the profiles which were obtained for the various influent and
effluent samples that were fractionated into "acids"/"neutrals" and bases.
Figures Al through A3 present the results for a solvent blank chromatographed,
on a fused silica capillary. The total ion profiles and single ion profiles
are also presented in these figures.
Figures A4 through A6 present the results for the neutral fractions for
Influent No. 2 to the superchlorination process. Virtually no components
were detected in the electron impact mode; however, a small number of
components were detected in the negative ion chemical ionization mode (Fig.
A5 and A6). In Figure A6 the single ion profiles represent the isotopic
forms 35 and 37 for chlorine and 79 and 81 for bromine. From the single ion
profiles of Figure A6, it is readily evident that a few peaks were detected
which were chlorinated compounds. Figures A7 through A9 present the results
of the neutral fraction for Influent No. 3. Again very few chlorinated
compounds were detected.
In contrast, the analysis of a neutral fraction for Effluent No. 1 from
the superchlorination process indicated the presence of many chlorinated
compounds as depicted in Figures A10 through A12. Similarly, the
74
-------
Table 30. LEVELS OF SELECTED "PURGEABLE" ORGANICS IN LIQUID SLUDGE BEFORE AND AFTER
SUPERCHLORINATION AT THE ROCKY MOUNT, NC FACILITYa
Compound
Ch Jerome thane
Dichlorodifluoromethane
Bromoethane
Methylene chloride
Trichlorofluorome thane
1,1-Dichloroethylene
1,1-Dichloroethane
Freon 113
Chloroform
1,1,1-Trichloroethane
-J
Cn
Carbon tetrachloride
Brofflodichloromethane
trans- 1,3-Dichloropropene
Trichloroethylene
Benzene
1,1,2, 2-Tetrachloroethene
1,1,2, 2-Tetrachloroethane
Toluene
Chlorobenzene
RINP/1S
20 +_ 15
8+8
3 + 2
260 + 110
390 +_ 229
10+3
24 + 22
15 ^ 2
9 + 7
175 +• 51
ND
ND
ND
86 +_ 5
50 +_ 23
139 + 32
ND
778 +_ 64
ND
REFF/1S
32 + 9
27 i 8
T
376 + 12
118 +_ 26
16 i 2
39 + 10
14+1
1,037 ^ 140
211 ^ 23
847 + 47
ND
9 + 7
81 + 1
48 +_ 20
182 + 18
ND
1,213 +_ 66
15 +_ 1
RINF/2S
54 +_ 32
4 + 4
T
203 +_ 40
74 +_ 26
9 i l
41 + 41
11^0
6 + 5
69 + 34
ND
ND
ND
66 +_ 1
354 + 279
102 + 24
ND
1,432 +_ 127
11 +_ 11
ppbb
REFF/2S
15 ^ 1
20 + 4
T
264 +_ 27
276 + 86
15 + 3
32 + 6
15 +^ 5
1,104 + 125
179 + 17
989 + 135
6 + 4
10 + 8
85 +_ 10
39 +_ 11
149 ^ 10
T
739 ^ 14
16+1
RINF/3S
18 + 8
12 + 4
ND
301 +_ 24
223 +_ 154
30 *_ 1
17 + 14
13 ^ 2
6+1
2 +_ 1
2 i 2
ND
T
69 + 13
61 + 24
36 +^ 1
ND
6,710 + 154
T
REFF/3S
11 + 5
17 + 7
T
267 + 67
212 t 78
12 + 3
18 + 7
19 + 8
912 ^ 312
130 + 55
792 + 317
-T
22 t_ 20
79 ^ 14
38 + 15
92 + 27
ND
1,187 + 357
8 1 7
Bed Samples
27 +_ 5
14 + 1
T
338 + 28
135 + 50
15 +_ 5
15 +_ 4
12 1 1
490 *_ 110
86 + 28
395 +_ 140
ND
T
73 + 18
45 +_ 12
106 + 34
ND
2,165 + 644
12 ^ 2
(continued)
-------
Table 30 (cont'd.)
Compound
Ethylbenzene
p_-Ch lorotoluene
Dichlorobenzene isoraer
RINF/1S
9 +_
ND
11 +
8
10
REFF/1S
13 +_ 1
951 +_ 90
25 +_ 1
RINF/2S
6 + 6
T
9+^9
ppbb
REFF/2S
12
1,586
32
+
+
+
0
269
1
RINF/3S
19 + 0
7 + 4
33 +_ 2
REFF/3S
12
1,620
26
+_ 1
^ 533
+ 8
Bed Samples
14 +_ 0
762 +_ 273
23+8
aSee Table 20 for sampling protocol, INF = influent liquid sludge, EFF = effluent liquid sludge,
b.
Based upon total sample.
-------
Table 31. EXTRACTS AND FRACTIONS PRODUCED DURING SAMPLE PROCESSING FOR EXTRACTABLES
(FAYETTEVILLE, NC)
Neutrals
Sample Code Bases
Pre-window Window Post-window Pre-window Window Post-window Nonpolar Polar
(GPC) (GPC) (GPC) (GPC) (GPC) (GPC) (Silica) (Silica)
INF1 GPA-1 "Acids" GPA-3 GP1 "Neutrals" GP4 SI S3 Bases
IMF2 GPA-2 " GPA-3
IHF3 GPA-1 " GPA-3 " " " " " "
EFF1 GPA-1
EFF2 GPA-1
EFF3 GPA-1
BED GPA-1 " " " " " " " "
-------
chromatograms of neutral fraction for Effluent No. 2 are given in Figures
A13 through A15 and again many chlorinated hydrocarbons were detected,
particularly when the negative ion chemical ionization mode was employed.
For Effluent No. 3 only a few compounds could be detected in the electron
impact mode; however, using negative ion chemical ionization MS many chlorina-
ted organics were uncovered (Fig. 16-18).
A sample from the settling bed for the superchlorination process was
analyzed and the results for the neutral fraction are given in Figures A19
through A21. Again chlorinated organics were detected as clearly shown in
Figures A20 and A21; however, their concentrations appeared considerably
lower than those in the immediate effluent from the process.
The acid fraction was also analyzed in the electron impact and negative
ion chemical ionization modes for each of the influent and effluent samples.
The results for the acid fraction for the Influent Nos. 1-3 are given in
Figures A22 through A30. Several chlorinated organics were detected. These
compounds appeared at different retention times than those which were detected
in the electron impact mode and thus it was concluded that the early eluting
chromatographic peaks in Figure A22 were predominately non-chlorinated
compounds. These observations were verified when the electron impact/positive
ion mass spectra of these chromatographic peaks were examined. Influent
Nos. 1-3 are contrasted by Effluent No. 1, iL.£., the acid fraction results
are given in Figures A31 through A33. Again, many chlorinated organics were
detected in this sample. The early eluting peaks in Figure A31 were predomi-
nantly non-chlorinated organics; however, minor chlorinated components did
appear at those chromatographic retention times. Similar results were
obtained for the acid fractions obtained from Effluent Nos. 2 and 3 (Fig.
A34-A39). The chromatographic profiles for the acid fraction obtained from
the settling bed sample from the superchlorination process were very similar
to those obtained for the effluents (Fig. A40-A42). The chromatograms for
the acid solvent blank contained trace chlorinated impurities (Fig. A43-
A45).
In addition to the fractions which are routinely generated for the
analysis of sludge samples by the standard currently available Priority
Pollutant protocol, the fractions which are normally excluded by the protocol
78
-------
were analyzed. The results for the GP1 neutral fraction for Influent No. 2
are given in Figures A46-A48. Several chlorinated organics were detected in
this fraction prior to the superchlorination process. The GP4 neutral
fraction for the sample Influent No. 2 sample was also analyzed by chromato-
graphing the sample on an SP-2100 coated fused silica capillary (A49-A51).
The results for the GP4 neutral fraction for Influent No. 3 sample are given
in Figures A52-A54. Few chlorinated organics were detected. In contrast,
the GP1 neutral fraction for Effluent No. 2 and the GP4 neutral fraction for
the same effluent indicated the presence of many chlorinated organics (see
Figures A55-A60). Similar results were obtained for the GP1 and GP4 neutral
fraction for Effluent No. 3 (see Figures A61-A66). Chromatograms for the
GP1 and GP4 neutral fractions are depicted in Figures A67-A72.
Finally, the profiles depicted in Figures A73-A100 present the results
for the acid fraction for Influent Nos. 1-3 Effluent Nos. 1-3 and Blanks (GP1
and GP4) chromatographed on the SP-1240 DA packed column. Again many chlorina-
ted organics were detected.
Additional fractions which are not included as part of the analysis
when using the Priority Pollutant protocol were examined for the presence of
chlorinated organics in the influent and effluent from the superchlorination
process. The SI neutral THF fraction for Effluent No. 1 and the S3 neutral/
acetone fraction of effluent No. 1 from the superchlorination process were
analyzed and the results are given in Figures A101-A106. As indicated in the
chromatographic profile for these samples analyzed by negative ion chemical
ionization, many chlorinated organics were detected.
Because chlorinated cyclohexene derivatives could be formed as artifacts
of the work-up of the samples and since the extraction solvent, methylene
chloride, contains ~1% cyclohexene as a preservative, the residual chlorine
in the samples was quenched. Figures A107-A110 present the negative ion
chemical ionization profiles for the neutral fraction of Effluent No. 2 from
the superchlorination process which was divided into two aliquots. One had
been quenched with sodium thiosulfate (0.026 moles) in excess of the amount
of chlorinated material determined in these samples while the other aliquot
was not quenched. These two aliquots of Effluent No. 2 were then processed
according to the current Priority Pollutant protocol to generate the neutral
79
-------
fraction. These results indicate slight differences between two aliquots
and examination of the mass spectra (negative ion chemical ionization)
indicates that a number of the chlorinated cyclohexanes and cyclohexanols
are absent in the chlorine-quenched sample. This is consistent with the
previous studies which have indicated that methylene chloride when used in
the Priority Pollutant protocol in the extraction of neutral compounds can
have an appreciable quantity of cyclohexene which may become readily chlori-
nated in the presence of molecular chlorine in a water sample. The aliquot
which had been treated with sodium thiosulfate after organic extraction and
centrifugation had a yellow color and a characteristic sulfur odor. Attempts
to concentrate the organic extract of the thiosulfate-treated sample to two
milliliters for injection onto the gel fractionation column were complicated
by copious precipitation of low solubility sulfur. A majority of the solid
was removed by cooling the extract in a dry ice/acetone bath and filtering
it through a glass pipet containing glass wool. Nevertheless, the number of
peaks attributable to this artifact are few and the overwhelming majority
are apparently chlorinated materials which are appearing in the effluent
from the superchlorination process and not as an artifact of the storage and
workup of the sample.
Table 32 presents the differences between the unquenched and quenched
sample with regard to chlorinated cyclohexane derivatives.
An attempt was made to identify the chlorinated compounds present in
the neutral and acid fractions for the influent, effluent and settling bed
samples. These results are given in Tables 33 and 34. Considerable diffi-
culty was experienced in the identification of these compounds since their
concentrations were seemingly below the detection limit for electron impact
positive ion mass spectrometry and the fragmentation pattern for these
compounds in the negative ion chemical ionization mode was extremely simple
which precluded the identification of many constituents. Nevertheless, some
of the chlorinated materials have been identified.
80
-------
Table 32. COMPARISON OF CHLORINATED CYCLOHEXANES IN CHLORINE
QUENCHED AND UNQUENCHED SUPERCHLORINATION PROCESS SAMPLES
Compound Quenched Unquenched
Chlorocyclohexane
Chlorocyclohexanol - +
Dichlorocyclohexane(s) - +
81
-------
Table 33. CHLORINATED COMPOUNDS IDENTIFIED IN FAYETTEVILLE, NC - NEUTRAL FRACTIONS
00
Fraction
INF 2
INF 3
Bed
EFF 1
EFF 2
EFF 3
GP1 NEUT EFF 2
GP1 NEUT EFF 3
EFF 1-S1 cut/THF
Spectrum
Number
606
700
610
788
702
607
700
808
843
610
448
426
203
342
267
447
701
-
372
426
372
424
409
307
Compounds
pentachlorotoluene
C7H3C150
pentachlorotoluene
tetrachlorobiphenyl
C7H3C150
pentachlorotoluene
C7H3C150
C7H3C150
I>,£'-DDE
pentachlorotoluene
trichloropyridine (tent.)
dichloropyridine (tent.)
chlorotoluene
trichloroaniline
dichloroaniline
trichloropyridine
C7H3C150
-ND-
trichlorotoluene
C7H4C14
trichlorotoluene
C7n4Cl4
pentachlorotoluene
trichlorotoluene
Negative Ion Positive Ion
A B C B
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
A refers to SP2100 capillary column, B to SP2250 packed column.
3C refers to SP2100 capillary column, B to SP2250 packed column.
-------
Table 34. CHLORINATED COMPOUNDS IDENTIFIED IN FAYETTEVILLE, NC
ACID FRACTIONS
Spectrum Negative Positive
Fraction number Compound ion ion
EFF 2 acid 279 chlorophenol X
348 chlorophenylacetic acid X
420 trichlorophenol (tent.) X
83
-------
REFERENCES
Pellizzari, E. D. and L. Little. Collection and Analysis of Purgeable
Organics Emitted from Treatment Plants. EPA-600/2-80-017, March 1980.
215 pp.
Dobbs, R. A. and J. M. Cohen. Carbon Adsorption Isotherms for Toxic
Organics. EPA-600/8-80-023, April 1980. 323 pp.
Wise, R. H., T. A. Pressley, and B. M. Austern. Partial Characterization
of Chlorinated Organics in Superchlorinated Septages and Mixed Sludges.
EPA-600/2-78-020, March, 1978. 30 pp.
Bender, J. H. Evaluation of the Purifax Process for the Treatment of
Septic Tank Sludges. EPA/MERL RTP, June, 1975. 20 pp.
Welcher, F. J. (ed.), and T. S. Ma. Microdetermination of Chlorine,
Bromine, or Iodine by the Closed Flask Method. In: Standard Methods
of Chemical Analysis, 6th Ed., Vol. Two, Part A, pp. 389-392. D. Van
Nostrand Co., Princeton, NJ, 1963.
EPA Interim Protocol. "VIOO-Methods for Purgeable Organics in Sludge".
EPA/EMSL/CI, December, 1979.
EPA Interim Protocol. "BlOO-Methods for Semivolatile Organic Components".
EPA/EMSL/CI, December, 1979.
84
-------
APPENDIX A
GC/MS/COMP PROFILES OF FRACTIONS OBTAINED FOR SAMPLES FROM
FAYETTEVILLE, NC SUPERCHLORINATION PROCESS
85
-------
oo
i n r rr r i i t t ITT
Mass Spectrum No.
Figure Al. Electron Impact GC/MS/COMP profile of solvent blank (SP2100,
0.23 mm i.d. x 25 m fused silica capillary).
-------
oo
.8 -
11 i i •
KI
Mass Spectrum No.
Figure A2. Negative chemical ionization GC/MS/COMP profile of solvent blank (SP2100,
0.23 mm i.d. x 25 m fused silica blank).
-------
oo
00
79 81
Figure A3.
Mass Spectrum No.
Negative chemical ionization GC/MS/COMP single ion profiles (m/z^ 35, 37, 79, 81)
of solvent blank (SP2100, 0.23 mm i.d. x 25 m fused silica capillary).
-------
00
Is '\
1
» T i-f r~i
Mass Spectrum No.
Figure A4. Electron impact GC/MS/COMP profile of "Neutral" fraction for Influent No. 2 to super-
chlorination process (SP2100 Hewlett-Packard fused silica capillary - 0.23 mm i.d. x
25 m).
-------
VD
o
•fc1 Si1 k1 k"
Mass Spectrum No.
Figure A5. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction of Influent
No. 2 to superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused silica
capillary).
-------
BfcCS -
3 iv
Mass Spectrum No.
y™"T'
Figure A6. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79, 81) of
"neutral" fraction of Influent No. 2 to superchlorination process (SP2100, 0.23 mm i.d. x
25 m fused silica capillary).
-------
\
Mass Spectrum No.
Figure A7. Electron impact GC/MS/COMP profile for "neutral" fraction for Influent No. 3
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused silica
capillary).
-------
CO
Mass Spectrum No.
Figure A8. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for
Influent No. 3 from superchlorination process (SP2100, 0.23 mm i.d. x 25 m
fused silica capillary).
-------
vO
§ ^ I
Mass Spectrum No.
81
Figure A9. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79, 81)
of "neutral" fraction for Influent No. 3 from superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica capillary).
-------
f
I
-,t-r»T. -.,,-• 1-. ,-1-r-r^-r, . .-
ci b •
?, £ '4
Mass Spectrum No.
Figure A10. Electron impact GC/MS/COMP profile of "neutral" fraction for Effluent No. 1
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused silica
capillary).
-------
f!.
V-
ill
b s fe fe
to t± m **
Mass Spectrum No.
Figure All. Negative chemical ionlzation GC/MS/COMP profile of "neutral" fraction for
Effluent No. 1 from superchlorination process (SP2100, 0.23 mm i.d. x 25 m
fused silica capillary).
-------
35 37 79 81
Mass Spectrum No.
Figure A12. Negative chemical ionization GC/MS/COMP single ion profiles (m/z/ 35, 37, 79, 81)
of "neutral" fraction for Effluent No. 1 from superchlorination process (SP2100,
0.23 mm i.d. x 25 m fused silica capillary).
-------
lO
oo
.„,„__
Mass Spectrum No.
Figure A13. Electron impact GC/MS/COMP profile of "neutral" fraction for Effluent No. 2
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused silica capillary)
-------
IO
VO
111
k' k fc1 k
»* »x •> *•>
Mass Spectrum No.
Figure A14. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for
Effluent No. 2 from superchlorination process (SP2100, 0.23 mm i.d. x 25 m,
fused silica capillary).
-------
o
o
|-|||g £±4JjsJ
ERfecs •r"^""""v w' • • v
« 2 s s
k b
Mass Spectrum No.
Figure A15. Negative chemical ionization GC/MS/COMP single ion profiles (m/£ 35, 37, 79,
81) of "neutral" fraction for Effluent No. 2 from superchlorination process
(SP2100, 0.23 mm x 25 m fused silica capillary).
-------
Mass Spectrum No.
Figure A16. Electron impact GC/MS/COMP profile of "neutral" fraction for Effluent No. 3
from superchlorination process (SP2100, 0.23 mm i.d. x 25 m, fused silica
capillary).
-------
o
to
Mass Spectrum No.
Figure A17. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for
Effluent No. 3 from superchlorination process (SP2100, 0.23 mm i.d. x 25 m,
fused silica capillary).
-------
o
OJ
/ /
! I I k
Mass Spectrum No.
Figure A18. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79, 81)
of "neutral" fraction for Effluent No. 3 from superchlorination process (SP210U,
0.23 mm i.d. x 25 m fused silica capillary).
-------
o
•C-
•*•* . tyr tiTT-rr . t (^
I i
"ST
•m T ^T y t" -i *t ii -i-f-r-i-.' ,-t-rr t • rr r t-i t .- • rr rr . r i
1 § s I
Mass Spectrum No.
Figure A19. Electron impact GC/MS/COMP profile of "neutral" fraction for Settling Bed
Sample from superchlorination process (SP2100, 0.23 mm i.d. x 25 m fused
silica capillary).
-------
I,1 ........ V ........ V
SSS
I1 ........ 1' ........ I' ........ L'
SSRS
Mass Spectrum No.
i;
Figure A20. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for
Settling Bed Sample from superchlorination process (SP2100, 0.23 mm i.d. x
25 m fused silica capillary).
-------
o
ON
mi
„ RfetS "_~- ••••"•• t t-
b S 5
37
/
79 81
" ' o o t" ' ' ' ' o ' ' ' '"""I, ' ' ' ' S, I, 'a o 'o 1^1.... "-, ,^t
s ; z s K s s g ; s s s
Mass Spectrum No.
Figure A21. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79,
81) of "neutral" fraction for Settling Bed Sample from superchlorination process
(SP2100, 0.23 mm i.d. x 25 m fused silica capillary).
-------
o
—J
Mass Spectrum No,
Figure A22. Electron impact GC/MS/COMP profile of "acid" fraction for Influent No. 1 from super-
chlorination process (SP1240 DA packed column).
-------
o
00
in u 5
-liuj-
*-i o. p
u. in F
Mass Spectrum No.
Figure A23. Negative chemical ionization GC/MS/COMP profile of "acid" fraction
for Influent No. 1 from superchlorination process (SP12AO DA packed
column).
-------
o
10
35 37 79 81
Mass Spectrum No.
Figure A2A. Negative chemical ionization GC/MS/COMP single ion profiles (m/z_ 35, 37,
79, 81) of "acid" fraction for Influent No. 1 from superchlorination
process (SP1240 DA packed column).
-------
-E
C-
yi
Mass Spectrum No.
Figure A25. Electron impact GC/MS/COMP profile of "acid" fraction for Influent No. 2
from superchlorination process (SP1240 DA packed column).
-------
-JVj
. **
ill
Mass Spectrum No.
Figure A26. Negative chemical ionization GC/MS/COMP profile of "acid" fraction
from Influent No. 2 for superchlorination process (SP1240 DA packed
column).
-------
Sjjjgggg
Mass Spectrum No.
Figure A27. Negative chemical ionization GC/MS/COMP single ion profiles (m/£ 35, 37,
79, 81) of "acid" fraction for Influent No. 2 from superchlorination
process (SP1240 DA packed column).
-------
Mass Spectrum No.
Figure A28. Electron impact GC/MS/COMP profile of "acid" fraction for Influent No. 3
from superchlorination process (SP1240 DA packed column).
-------
a
Mass Spectrum No.
Figure A29. Negative chemical ionization GC/MS/COMP profile of "acid" fraction for
Influent No. 3 from superchlorination process (SP1240 DA packed column)
-------
t
U>0
fc
Oi or a a fv
Pf-'PP
S^^^
pu.b-u.ti.
Ol ** Z IT Z Z
a -1"""
Mass Spectrum No.
Figure A30. Negative chemical ionization GC/MS/COMP single ion profiles of "acid" fraction
for Influent No. 3 for superchlorination process (SP1240 DA packed column).
-------
r
r^rr™
Mass Spectrum No.
Figure A31. Electron impact GC/MS/COMP profile of "acid" fraction for Effluent No. 1 from super-
chlorination process (SP1240 DA packed column).
-------
tn
S
*§
a er—
ZP-|
lu u a
-JUJI-
Mass Spectrum No.
Figure A32. Negative chemical ionlzation GC/MS/COMP profile of "acid" fraction for
Effluent No. 1 from superchlorination process (SP1240 DA packed column).
-------
co
Figure A33. Negative chemical ionization GC/MS/COMP single ion profiles (m/jj 35, 37,
79, 81) of "acid" fraction for Effluent No. 1 from superchlorination
process (SP1240 DA packed column).
-------
Mass Spectrum No.
Figure A34. Electron impact GC/MS/COMP profile of "acid" fraction for Effluent No. 2
from superchlorination process (SP1240 DA packed column).
-------
1C g
Mass Spectrum No.
Figure A35. Negative chemical ionization GC/MS/COMP profile of "acid" fraction for Effluent
No. 2 from superchlorination process (SP1240 DA packed column).
-------
Mass Spectrum No.
Figure A36.
Negative chemical ionization GC/MS/COMP single ion profiles (m/z^ 35, 37, 79,
81) of "acid" fraction for Effluent No. 2 from superchlorination process
(SP1240 DA packed column).
-------
N3
*
»E
r-i-p
Mass Spectrum No.
Figure A37. Electron impact GC/MS/COMP profile of "acid" fraction for Effluent No. 3
from superchlorination process (SP1240 DA packed column).
-------
to
3P
K --
M:
in u a
Mass Spectrum No.
Figure A38. Negative chemical ionization GC/MS/COMP profile of "acid" fraction from
Effluent No. 3 from superchlorination process (SP1240 PA packed column).
-------
5
£
CD or ne of nr
u u u u
-------
to
l/l
Mass Spectrum No.
Figure A40. Electron impact GC/MS/COMP profile of "acid" fraction for Settling Bed Sample
from superchlorination process (SP1240 DA packed column).
-------
tsJ
t.B
Mass Spectrum No.
Figure A41. Negative chemical ionization GC/MS/COMP profile of "acid" fraction from
Settling Bed Sample for superchlorination process (SP1240 DA packed column)
-------
p UL U. U- U.
Rr«- tn —
n N. CD
Mass Spectrum No.
Figure A42. Negative chemical ionization GC/MS/COMP single ion profiles (m/z_ 35, 37, 79,
81) of "acid" fraction for Settling Bed Sample from superchlorination process
(SP1240 DA packed column).
-------
00
£
£
CM
IV- —
m
a:
-------
vo
en s>
z U)
CT
_l
tu
» i
cc
-------
LO
O
£
tn to
F™
CJ
U LJ
a - en
— a. o o o o
,/U^'YW^
79 8
-r-pr-r -i r-i ,-••-; |—r
Mass Spectrum No.
Figure A45. Negative chemical ionization GC/MS/COMP single ion profiles
(m/z_ 35, 37, 79, 81) of "acid" solvent blank (SP1240 DA packed
column).
-------
CO
Mass Spectrum No.
Figure A46. Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for
Influent No. 2 (SP2100 capillary).
-------
N>
9
«p
CD -*
S-S
zpj
m ^j ff
^juit-
~V
Spectrum No.
Figure A47. Negative chemical ionization GC/MS/COMP profile of GP1 "neutral
fraction for Influent No. 2 (SP2100 capillary).
-------
Mass Spectrum No.
Figure A48. Negative chemical ionization GC/MS/COMP single ion profiles (m/^ 35, 37,
79, 81) of GP1 "neutral" fraction for Influent No. 2 (SP2100 capillary).
-------
(^
3
>
*
v
-
IUU <
Hff
U.UI
Mass Spectrum No.
Figure A49. Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Influent No. 2 sample (SP2100 capillary).
-------
Cn
« S
M:
111 (_>
-------
-
tnoc at acac
u u u u
-------
u>
Mass Spectrum No.
Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Influent No. 3 sample (SP2100 capillary).
-------
00
2P
CD —
ID
S
V g
«c a —
Mass Spectrum No.
Figure A53. Negative chemical ionization GC/MS/COMP profile of GP4 "neutral"
fraction for Influent No. 3 (SP2100 capillary).
-------
oo
£8
is
p u
U
cc cc
M m tw S
J UJ Z Z Z Z
•- a. o o o o
u. in •—•-•-•-
35 37
81
Mass Spectrum No.
Figure A54. Negative chemical ionization GC/MS/COMP single ion profiles of "neutral"
fraction for Influent No. 3 sample (SP2100 capillary).
-------
Mass Spectrum No.
Figure A55. Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for Effluent No.
2 sample (SP2100 capillary).
-------
tf g -
-------
Mass Spectrum No.
Figure A57. Negative chemical ionization GC/MS/COMP single ion profiles of GP1
"neutral" fraction for Effluent No. 2 sample (SP2100 capillary).
-------
£
(no
Mass Spectrum No.
Figure A58. Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Effluent No. 2 (SP2100 capillary).
-------
•nE
8-
i
Mass Spectrum No.
Figure A59. Negative chemical ionization GC/MS/COMP profile of GP4 "neutral" fraction
of Effluent No. 2 (SP2100 capillary).
-------
Mass Spectrum No.
Figure A60. Negative chemical ionization GC/MS/COMP single ion profiles (m/z^ 35, 37, 79,
81) of GP4 "neutral" fraction of Effluent No. 2 (SP2100 capillary).
-------
Mass Spectrum No.
Figure A61. Electron impact GC/MS/COMP profile of GP1 "neutral" fraction for Effluent
No. 3 (SP2100 capillary).
-------
tse
m —
V E
tL OC •-*
Mass Spectrum No.
Figure A62. Negative chemical ionization GC/MS/COMP profile of GP1 "neutral" frac-
tion of Effluent No. 3 (SP2100 capillary).
-------
•e-
00
«-• ft. o o oo
u.m —— ——
Mass Spectrum No.
Figure A63. Negative chemical ionization GC/MS/COMP single ion profiles (m/_z 35, 37, 79,
81) of GP1 "neutral" fraction for Effluent No. 3 (SP2100 capillary).
-------
Mass Spectrum No.
Figure A64. Electron impact GC/MS/COMP profile of GP4 "neutral" fraction for
Effluent No. 3 sample (SP2100 capillary).
-------
V §
-------
•- o. o o o o
Mass Spectrum No.
Figure A66. Negative chemical ionization GC/MS/COMP single ion profiles (m/£ 35, 37, 79,
81) of GP4 "neutral" fraction for Effluent No. 3 (SP2100 capillary).
-------
Ul
Mass Spectrum No.
Figure A67. Electron impact GC/MS/COMP profile of GP1 "neutral" solvent blank (SP2100
capillary).
-------
u>
se s
Mass Spectrum No.
Figure A68. Negative chemical ionization GC/MS/COMP profile of GP1 "neutral" solvent
blank (SP2100 capillary).
-------
Q-I
"If'-l
A»* <»• » — c^yV'
/ /
• /•*' «/! • - -- -i. •..
Figure A69.
Mass Spectrum No.
Negative chemical ionization GC/MS/COMP single ion profiles (m/^ 35, 37,
79, 81) of GP1 "neutral" solvent blank (SP2100 capillary).
-------
Ln
Mass Spectrum No.
Figure A70. Electron impact GC/MS/COMP profile of GP4 "neutral" solvent blank
(SP2100 capillary).
-------
1/1
ON
'.M--"^
Mass Spectrum No.
Figure A71. Negative chemical ionization GC/MS/COMP profile of GP4 "neutral" solvent
blank (SP2100 capillary).
-------
35
JV*"<*T'ln«f-lr-l''['.71'.!.-v-l«W.t<<
Mass Spectrum No.
Figure A72. Negative chemical ionization GC/MS/COMP single ion profiles of GPA "neutral"
solvent blank (SP2100 capillary).
-------
00
5
i
U..L
TTTT I |'T"1 I*^TTT : 1 |" I r~f r
Mass Spectrum No.
"I"
Figure A73. Negative chemical ionization GC/MS/COMP profile of GPA 1 "acid" fraction for
Influent No. 1 sample from superchlorination process.
-------
l/l
VD
*~""rt-t i T T-» 'i ? |'t T ? -I Ti-t-r t-y-t ft t-r FT I--T ft -r-f i
-i-t-T-|~r rt i-t i i i i | f t « i T ?-»• T-T-f-rt-r ri-r-r-rt i r i i rt t r t T'j't-i
o o o o o
•> ** rv « n
Mann SpcctTum Wo.
pr r-r^i-f-f*
Figure A74. Negative chemical ionization GC/MS/COMP single ion profiles (m/z^ 35, 37,
79, 81) of GPA 1 "acid" fraction for Influent No. 1 sample from
superchlorination process.
-------
OS
o
I
VA
Mans Spectrum No.
Figure A75. Electron impact GC/MS/COMP profile of GPA 1 fraction for Influent No. 2 from
superchlorination process.
-------
r——~*v«-Ju-.
-'«J--— K „ _*^_J~,--W_J^-
t | r t-rt . . -i-ti r-i-» t-r »-r n T-I- . • T-r-t-Tri i-pi
0000
Z 1 Z Z
Mans Spectrum No.
ri IT t r f T'* r-rrr T f-r i (^
rr-f n t-rt
Figure A76. Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction for Influent
No. 2 from superchlorination process.
-------
S3
t
is
£
*
P
a
T\l
"'I'll if f
rf™r^w^
^Vw ji H
!'^PH^^^1W^^W^,M^
o
(J
u>
o
o
o
Ilass Spectrum No.
Figure A77. Negative chemical ionization GC/MS/COMP single ion profiles (m/_z 35, 37, 79, 81) of
GPA 1 fraction for Influent No. 2 from superchlorination process.
-------
ON
LO
T L1 'o1
o p o
*» * 10
Mass Spectrum No.
Figure A78. Electron impact GC/MS/COMP profile of GPA 1 fraction for Influent No. 3 from superchlorination
process.
-------
S,
Mass Spectrum No.
Figure A79. Electron impact GC/MS/COMP profile of GPA 1 for Effluent No. 2 from superchlorination
process.
-------
o\
Ln
...1
Mn«s Spectrum No.
Figure A80. Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction for Effluent
No. 2 from superchlorination process.
-------
*
c
5
_.— — __ ftfc -_ ^. '*-'*• _ __ ^-
'
Mass Spectrum No.
Figure A81. Negative chemical ionization GC/MS/COMP single ion profile (m/z 35, 37, 79, 81) of
GPA 1 fraction for Effluent No. 2 from superchlorination process.
-------
LA *.
JL.
Mass Spectrum No.
Figure A82. Electron impact GC/MS/COMP profile of GPA 1 fraction from Effluent No. 3 for superchlorination
process.
-------
00
*
I.
I I
Maos Spectrum No.
Figure A83. Negative chemical ionization GC/MS/COMP profile of GPA 1 fraction for Effluent No. 3
from superchlorination process.
-------
ON
VD
*
I
Mass Spectrum No.
Figure A84. Negative chemical ionization GC/MS/COMP single ion profiles (m/z^ 35, 37, 79, 81) for
Effluent No. 3 from superchlorination process.
-------
--J
o
'l,111
k k k s k k 's k k
Mr>«inwr\.iBno
Mass Spectrum No.
Figure A85. Electron impact GC/MS/COMP profile of GPA 1 "blank".
-------
T I"
s ?
Maso Spectrum No.
Figure A86. Negative chemical ionization GC/MS/COMP profile of GPA 1 for "blank".
-------
to
H^^r^wV^
I I I i I I I I
Mass Spectrum No.
Figure A87. Negative chemical ionization GC/MS/COMP profiles (m/z 35, 37, 79, 81) of
GPA 1 for "blank". ~
-------
U!
Mass Spectrum No.
Figure A88. Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent No. 2 from
superchlorination process.
-------
*
i.
r" pf i-fi""1 r-i-i
Mass Spectrum No.
Figure A89. Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction for Influent No. 2
from superchlorination process.
-------
01
>^^^
trv
Mass Spectrum No.
Figure A90. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79, 81)
of GPA 4 fraction for Influent No. 2 from superchlorination process.
-------
rr-i-rr-r-ri r
^^S
Mass Spectrum No.
Figure A91. Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction for Effluent No. 2
from superchlorination process.
-------
—J
—4
i/l
111
Mass Spectrum No.
Figure A92. Electron impact GC/MS/COMP profile of GPA k for Effluent No. 2 from superchlorination
process.
-------
•-J
co
p-r-| rrr-i~«-
Mass Spectrum No.
Figure A93. Negative chemical ionization GC/MS/COMP single ion profiles of GPA 4 fraction for
Effluent No. 2 from superchlorination process.
-------
--J
VD
*. A < . -.1
rTr
Mass Spectrum No.
Figure A94. Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent No. 3 from
superchlorination process.
-------
00
o
*
\
Mass Spectrum No.
Figure A95. Electron impact GC/MS/COMP profile of GPA 4 fraction for Influent No. 3 from
superchlorination process.
-------
00
W
-------
00
to
I*
t I - -••— - - — -— — - - - - -~ .
—f.-T-r-rrr-rrp-r-i-i-t-. n i-pi • •>-. IITI ? p-r . . . . i •-. | . -. .-i t i i i • \ • • i i T , r-i i-f i • •• T i . .-ft p r i , i t-< t . ( . i . .-r ti-r ry . t . • r n . j-t 1-1 r n-i-rr p-r i i • r i i
* aoooooooooo
2Sr!?K«»t^o>«o-
Spectrum No.
Figure A97. Negative chemical ionization GC/MS/COMP profile of GPA 4 fraction for Effluent No. 3
from superchlorination process.
-------
00
9
I
r n T- t-r- r~t T f 1
Mass Snoctrntn No.
Figure A98. Negative chemical ionization GC/MS/COMP profile single ion profiles (m/z 35, 37,
79, 81) of GPA 4 fraction for Effluent No. 3 from superchlorination process.
-------
00
.p-
1-J-! ..........
Mass Spectrum No.
Figure A99. Negative chemical ionization GC/MS/COMP profile of GPA 4 "blank".
-------
00
'Pit
luV^v^11^
Mass Spectrum No.
Figure A100. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79, 81) of
GPA 4 "blank".
-------
oo
£
in CD
E.i
Mass Spectrum No.
Figure A101. Electron impact GC/MS/COMP profile of Si-neutral THF fraction for
Effluent No. 1 (SP2100 capillary).
-------
00
u u cc
_JUJl-
u. tn f-
Figure A102.
Mass Spectrum No.
Negative chemical ionization GC/MS/COMP profile of Sl-THF fraction
for Effluent No. 1 (SP2100 capillary).
-------
oo
oo
Mass Spectrum No.
Figure A103. Negative chemical ionization GC/MS/COMP single ion profiles (m/£ 35, 37,
79, 81) of Sl-THF fraction for Effluent No. 1 (SP2100 capillary).
-------
00
vo
Mass Spectrum No.
Figure A104. Electron impact GC/MS/COMP profile of S3-neutral acetone fraction of
Effluent No. 1 (SP2100 capillary).
-------
VO
O
£
tno
Mass Spectrum No.
Figure A105. Negative chemical ionization GC/MS/COMP profile of S3-neutral acetone
fraction for Effluent No. 1 (SP2100 capillary).
-------
vr>
eeeg
LJ (J U O
-------
VO
N)
\
Mass Spectrum No.
Figure A107. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for Effluent No. 2
from superchlorination process (C19 unquenched in sample).
-------
Mass Spectrum No.
Figure A108. Negative chemical ionization GC/MS/COMP profile of "neutral" fraction for
Effluent No. 2 from superchlorination process (€!„ quenched in sample).
-------
VO
Figure A109.
Hass Spectrum No.
Negative chemical ionization GC/MS/COMP for ion profiles (m/z 35, 37, 79, 81)
of "neutral" fraction for Effluent No. 2 from superchlorination process (Cl~
quenched in sample).
-------
VO
Cn
Mass Spectrum No.
Figure A110. Negative chemical ionization GC/MS/COMP single ion profiles (m/z 35, 37, 79,
of "neutral" fraction for Effluent No.
sample unquenched).
81)
2 from superchlorination process (Cl_ in
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
4. TITLE AND SUBTITLE
VOLATILE ORGANICS IN AERATION GASES AT MUNICIPAL
TREATMENT PLANTS
7. AUTHOR(S)
Edo D. Pellizzari
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, NC 27709
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, OH 45268
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
June, 1981
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT
31U-1781
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2780
13. TYPE OF REPORT AND PERIOD COVEI
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Utilizing previously developed and validated analytical methods, research was
conducted to: (1) estimate volatile (purgeable) Priority Pollutants stripped from
aeration basins at a Municipal Wastewater Treatment Facility; (2) determine the vola
tile Priority Pollutants in wastewater and activated sludge of a treatment facility;
(3) determine the equilibrium distribution of volatile Priority Pollutants between tl
solid and aqueous phases for wastewater and activated sludge; (4) measure volatile
pollutants produced by stabilization of sludge by superchlorination; and (5) deter-
mine, if any, the chlorinated organics produced during superchlorination of sludge.
Liquid and gas sampling strategies were developed to obtain representative data on tl
emission of purgeable Priority Pollutants from aeration basins of a municipal waste-
water treatment facility.
This report was submitted in fulfillment of Contract No. 68-03-2780 by the
Research Triangle Institute under the sponsorship of the U. S. Environmental Protec-
tion Agency.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Priority Pollutants
Quantitation
Off-gas
Municipal Wastewater
Activated Sludge
IB. DISTRIBUTION STATEMENT
b-IDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (This Report)
20. SECURITY CLASS (This page)
c. COSATl Field/Grou
21. NO. OF PAGES
212
22. PRICE
EPA Form 2220-1 (R«v. 4-77) PREVIOUS EDITION it OBSOLETE
196
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