United States
Environmental Protection
Agency
Municipal Environmental Research EPA 600 2-79-006
Laboratory March 1979
Cincinnati OH 45268
Research and Development
Selected
Biodegradation
Techniques for
Treatment and/or
Ultimate Disposal of
Organic Materials
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EPA-600/2-79-006
March 1979
SELECTED BIODEGRADATION TECHNIQUES FOR
TREATMENT AND/OR ULTIMATE DISPOSAL OF
ORGANIC MATERIALS
by
SCS Engineers
Long Beach, California 90807
Contract No. 68-03-2475
Project Officer
Charles J. Rogers
Solid and Hazardous Waste 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.
n
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the American people. Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solution
and it involves defining the problem, measuring its impact, and searching for
solutions. The Municipal Environmental Research Laboratory develops new and
improved technology and systems for the prevention, treatment, and management
of wastewater and solid and hazardous waste pollutant discharges from munici-
pal and community sources, for the preservation and treatment of public drink-
int water supplies, and to minimize the adverse economic, social, health, and
aesthetic effects of pollution. This publication is one of the products of
that research; a most vital communications link between the researcher and
the user community.
Organic constituents in aqueous process effluent from various industries
often have properties not readily treatable by conventional biological pro-
cesses. These properties include high COD/BOD ratios, low nutrient content,
biocidal content, marginally degradable constituents, and a tendency toward
highly variant concentrations (shock loading). For this reason, research was
conducted to identify, characterize, and compare types of biological treat-
ment processes and operational methods that successfully handle problematic
organic industrial waste.
Francis T. Mayo, Director
Municipal Environmental
Research Laboratory
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ABSTRACT
Organic constituents in aqueous process effluent from various
industries often have properties not readily treatable by conven-
tional biological processes. These properties include high
COD/BOD ratios, low nutrient content, biocidal content, marginally
degradable constituents, and a tendency toward highly variant con-
centrations (shock loading). For this reason, research was con-
ducted to identify, characterize, and compare types of biological
treatment processes and operational methods that successfully han-
dle problematic organic industrial waste. The objectives of the
technology comparison are to identify the most robust biological
treatment techniques (applicable to the broadest range of waste
classes) and to describe those treatment characteristics that
specifically enhance biodegradation of organic waste. Design,
performance, and economic comparisons of the studied biological
treatment technologies are presented to assist waste managers and
engineers In the selection of proper treatment methods.
Additional research was conducted in order to determine the
removal efficiency of hazardous organic materials at three dif-
ferent biological treatment facilities (activated sludge, series
lagoons, and deep shaft aeration). The data were used to compare
influent and effluent loading of hazardous organics for removal
efficiencies and the concentration of hazardous organics in the
waste biological sludge. The concentration of any one hazardous
organic in the waste did not exceed 2 mg/ju and the majority was
present in the 1-100 yg/£ range. The series lagoons systems demon-
strated the best assimilation of the largest variety of hazardous
organics. The varied biochemical reactions facilitated by each
lagoon environment and extended retention period are suggested as
determining factors. Analysis of biological sludges from the
studied facilities indicates the tendencies of these materials to
adsorb hazardous organics intact. •
This report was submitted in fulfillment of Contract 68-03-
2475 by SCS Engineers under the sponsorship of the U.S. Environ-
ment Protection Agency. This report covers the period September
1976, to July 1978, and work was completed as of September 15,
1978.
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CONTENTS
Page
Foreword iii
Abstract iv
Figures vii
Tables xi
Acknowledgements xviii
Section
I Introduction 1
II Conclusions and Recommendations 5
III Literature Review 10
t The Waste Stream 10
t General Waste Qualities 31
• Classes of Organic Wastes Not Amenable 37
to Biodegradation
• Required Degree of Treatment 40
• Practical Applications of Biodegradation 55
of Organic Industrial Wastes
• Microbial Assimilation of Organic Wastes 96
IV Site Studies 103
• Gulf Coast Waste Disposal Authority (GCWDA) 105
40-Acre Industrial Waste Treatment Facility,
Texas City, Texas
• Gulf Coast Waste Disposal Authority (GCWDA) 161
Washburn Tunnel Industrial Waste Treatment
Facility, Pasadena, Texas
t ICI Deep Shaft Aeration Process, Paris, Ontario, 204
Canada
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CONTENTS (continued)
Section Page
• An Eastern Chemical Production Plant (UNOX) 235
Faci1ity
V Sampling Activities 267
• 40-Acre Facility 269
• Washburn Tunnel Facility 282
• Deep Shaft Facility 295
VI Engineering and Economic Comparisons of Identified 305
Biodegradation Techniques
VII References 321
Appendices
A. Bibliography of pertinent literature pertaining 337
to microbial degradation of organics
B. Sampling and Analysis: Parameter and Station Selection 342
• Selection of organic toxins for Sampling and 342
analysis
• Selection of Biological parameters for analysis 342
• Station selection and sampling frequency 350
• Sampling Methods 350
t Analytical Methods 355
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FIGURES
Number Page
1 Sources of organic and inorganic waste streams 11
from various industries
2 Classification of organic compounds which may occur 16
in petrochemical waste streams
3 Clarification of inorganic compounds which may occur 18
in petrochemical waste streams
4 Effluent characteristics: bleached kraft mill 24
5 Flow rates in coal gasification 30
6 A Rhode Island textile industry effluent profile: 33
COD, BOD, and suspended solids versus time
7 Example of a deep shaft aeration plant treatment 64
scheme
8 Schematic diagram of three-stage UNOX system 66
9 Two stages of anaerobic waste stabilization 74
10 Possible biological and chemical reactions in 76
anaerobic treatment lagoon processes
11 Aerobic activated carbon treatment/regeneration: 85
schematic flow diagram
12 GCWDA 40-Acre facility layout 106
13 Location of GCWDA 40-Acre facility 108
14 Location of industries supplying influent to 110
40-Acre facility
15 Historical representation of waste streams 111
entering the GCWDA 40-Acre treatment facility
16 Anaerobic-aerobic demonstration system for 126
determining waste treatment design at 40-Acre
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FIGURES (continued )
Number
Page
17 GCWDA 40-Acre facility layout: schematic 133
diagram
18 40-Acre distribution piping 135
19 Ashbrook mechanical surface aerator - high speed 137
(MSAH)
20 COD removal as a function of loading and 139
temperature
21 Relationship between BOD and COD removal 140
22 Effect of lagoon depth on COD removal and 141
sulfide level
23 Effect of additional aeration on aerated 143
stabilization effluent
24 Relationship of lagoon feed and effluent solids 144
levels
25 Location of monitoring hardware 147
26 Maps of Houston, Texas, and vicinity 163
27 Map of Washburn Tunnel 164
28 Washburn Tunnel facility influent concentrations 181
(ppm) monthly influent/effluent reports - 1976
29 Influent to Washburn Tunnel treatment plant 182
1976 (Ibs/day)
30 Process flows through the GCWDA Washburn Tunnel 185
facility
31 Washburn Tunnel facility cooling tower 187
32 Washburn Tunnel facility: GCWDA existing 190
sampling stations
33 Washburn Tunnel facility effluent concentrations 197
(ppm) monthly influent/effluent reports - 1976
34 Effluent from Washburn Tunnel treatment plant 198
viii
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FIGURES (continued)
Number Page
35 Washburn Tunnel facility: Approximation of 200
nutrient balance
36 Paris, Ontario: Regional map 206
37 Paris, Ontario: Local map 207
38 BOD loading rates 211
39 Plan view of the Deep Shaft facility 213
40 Sketch of Deep Shaft structural housing 214
41 Sealing of the Deep Shaft conduit 216
42 Paris, Ontario Deep Shaft flow diagram 218
43 Deep Shaft daily data log 222
44 Deep Shaft daily digestor data log 223
45 Schematic of wastewater flow through UNOX plant 239
46 Schematic diagram of UNOX system 241
47 Flow control and mixing in the UNOX system - 242
overhead view
48 Flow diagram of a "lindox" PSA oxygen 246
generating system
49 UNOX system removal efficiencies - (MLVSS used 255
in F/M calculations)
50 UNOX system removal efficiencies - BODg and COD 256
vs. siudge age
51 UNOX system effluent quality vs. F/M ratio 257
(MLVSS used in F/M calculations)
52 UNOX system effluent quality vs. sludge age 258
53 GCWDA 4-Acre Facility layout, and sampling sites 272
54 Washburn Tunnel Facility layout and sampling sites 285
55 Paris Deep-Shaft Facility 297
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FIGURES (continued)
Number Page
56 Approach to comparisons of studied technologies 307
57 Two conceptual industrial waste treatment systems 315
utilizing primary aerobic evaluation-stabilization
units
B-2 Location of control and outfall sediment sampling 351
sites
B-3 Hypothetical fluctuation of one constituent in- 352
plant influent-effluent
B-4 Composite sampler equipment 354
B-5 Grab sampler equipment 356
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TABLES
Number Page
1 Quantity of Potentially Hazardous Waste and 14
Hazardous Constituents Generated by the Petroleum
Refining Industry
2 Industrial Wastewater Oxygen Demand and Organic 17
Carbon
3 Hazardous Wastes Generated by the Pharmaceutical 20
Industry
4 Summary of Typical Types of Organic Pharmaceutical 21
Hazardous Waste Materials
5 Drug Manufacturing Wastes 23
6 1972 Production by Pulp Type and Paper Grades 26
7 Typical Analysis of Ammoniacal Liquor and Still 27
Waste
8 Analyses of Coke Oven Liquors by the British 28
Coke Research Association
9 A Rhode Island Dyehouse Raw Waste Profile and 32
Dyeing Cycle Components
10 Problem Concentrations of Tested Materials as 38
Determined by Manometric Investigations
11 Biological Degradabi1ity of Aromatic Compounds 41
12 Biological Degradabi1ity of Cycloaliphatic 44
13 Biological Degradabi1ity of Aliphatic Compounds 45
14 Comparison of COD, BOD, and ThOD with Respect 46
to Theoretical Organic Chemicals
15 Treatment Plant Survey Data 49
16 BPCTCA Effluent Limitations in kg/t 51
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TABLES (continued)
Number Page
17 Maximum Thirty-Day Average Effluent Limitations 53
Guidelines: Iron and Steel Industry
18 Maximum Thirty-Day Average Effluent Limitations 54
Guidelines: Textile Mills for July 1, 1977
19 Applications of Conventional Treatment Schemes 56
to Various Organic Industrial Wastes as Reported
in the Literature
20 Applications of Innovative Treatment Schemes 59
to Various Organic Wastes as Reported in the
Literature
21 Operating Conditions and Plant Efficiencies for 65
Two Deep Shaft Aeration Plants
22 Comparisons of Process Design Conditions for 68
the UNOX System and for Conventional Air Aeration
Systems for Typical Municipal Wastewater
23 UNOX vs. Conventional Air Activated Sludge 69
24 Summary of UNOX System Experience with Chemical 70
and Petrochemical Wastes
25 Phenol Degradation Rates in Tapered Fluidized 73
Bed Bioreactor
26 Removal of Specific Organics in Anaerobic Lagoons 77
27 Data from Union Carbide Pilot and Full-Scale 79
Studies
28 Construction Cost Summay Anaerobic-Aerated 81
Stabilization System
29 Estimated Operating Cost Anaerobic-Aerated 82
Stabilization System
30 Experimental Results on the Octanol Plant Waste 84
Treatment by Various Processes
31 Carbon Addition to Activated Sludge - DuPont 93
PACT Process
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TABLES (continued)
Number Page
32 List of Microorganisms Reported by Various Authors 97
to Assimilate Recalcitrant Organic Materials
33 Microorganisms Known to Metabolize Organochlorine 101
Pesticides
34 Characterization of Influent A 112
35 Characterization of Influent A Loading to the 113
40-Acre Facility
36 Character ization of Influent B, 115
37 Character ization of Influents 116
38 Characterization of Influent B Loading Values 117
39 Characterization of Influent C 118
40 Characterization of Influent C Loading Values 119
41 Characterization of Influent D 121
42 Characterization of Influent D Loading Values 122
43 Treatment Considerations at GCWDA 123
44 Systems Studied for Application at 40-Acre 124
45 Combined Influent A, B, and C Loading Values 127
and Their Relationship to Required Nutrients
46 Combined Influent A, B, C, and D Loading Values 128
and Their Relationship to Required Nutrients
47 Dischargers 1 and 2 Influent Monitoring 129
Requi rements
48 Discharger 3 Influent Monitoring Requirements 130
49 Dischargers 1, 2, and 3 Influent Limitations 131
In Kg/day (Ib/day) Effective July 1, 1977
50 40-Acre Basin Dimensions and Retention 134
51 Ashbrook MSAH 75/900 Characteristics 138
XI 1 1
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TABLES (continued)
Number Pa9e
52 GCWDA 40-Acre Operational Modes as of February 146
1975
53 40-Acre Facility: Anaerobic Lagoon 148
54 40-Acre Facility: Limited Aeration Basin 149
Effluent Quality
55 Aerated Stabilization Basins F/M Ratios From 150
1975-1976
56 40-Acre Facility: Aerated Stabilization Basins 151
(ASB) Monitoring Data (1975)
57 40-Acre Facility: Aerated Stabilization Basins 152
(ASB) Monitoring Data (1976)
58 TWQB Daily Average Effluent Loading Discharge 153
Limitations: 8/75-7/77, and the Corresponding
Monthly 40-Acre Effluent Loading Discharge for
8/75-3/77
59 TWQB Effluent Loading Discharge Limitations 154
Effective 7/1/77
60 Average Wastewater Constituent Removal 156
Efficiency - May 1975 through December 1976
61 Major Assumptions of the Construction Cost 158
Estimate
62 Construction Cost Estimate: Anaerobic-Aerated 159
Stabilization System
63 Temperatures in the Gulf Coast Retion of Texas 166
64 1976 Summary - Washburn Tunnel Facility: Influent 168
Wastes
65 1976 Summary - Washburn Tunnel Facility: Influent 170
Wastes (kg/day)
66 1976 Influent Summary - Washburn Tunnel 173
67 "1976 Influent Summary - Washburn Tunnel (kg/day) 174
xiv
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TABLES (continued)
Number
68 NPDES Effluent Limitations for the Washburn 176
Treatment Facility - (Effective to kg/day (Ib/day)
June 30, 1977
69 Washburn Tunnel Facility: Averages of Reported 177
Monthly Maximum 1976 Influents
70 Required Levels of Treatment to Meet 1976 NPDES 178
Permit Effluent Limitations - Washburn Tunnel
Facility
71 Unit Capacities: Washburn Tunnel Facility 168
72 1976 Data for Primary Effluent and Aerator 179
73 Washburn Tunnel Facility - 1976 Effluent Quality 194
Summary
74 Washburn Tunnel Facility - 1976 Effluent Quality 195
Summary
75 Washburn Tunnel Facility: 1976 Overall Treatment 196
Plant Efficiency
76 Washburn Tunnel Facility: Estimated Construction 202
Cost Summary
77 Washburn Tunnel Facility: Estimated O&M 203
Costs - 1976
78 Deep Shaft Facility, Paris, Ontario: Weekday 209
(7 Day) Operation - March 4 - July 15, 1977
79 Deep Shaft Facility, Paris, Ontario: May 1977 210
Influent Monitoring Data
80 Deep Shaft Facility, Paris, Ontario: Weekend 226
Operation: March 4 - July 15, 1977
81 Deep Shaft Facility, Paris, Ontario: May 1977 227
Effluent Monitoring Data
82 BOD5 Removal Efficiency 228
83 COD Removal Efficiency 229
84 Suspended Solids Removal Efficiency 230
xv
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TABLES (continued)
Number Pa9e
85 Paris, Ontario Deep Shaft Facility: Estimated 233
Construction Cost Summary
86 Paris, Ontario Deep Shaft Facility: O&M Cost 234
1976
87 Clariflocculator 250
88 UNOX System 251
89 Plant Summary 253
90 Data on F/M Ratios and Corresponding Percent 259
Removals as Plotted in Figure 49
91 Data on Sludge Age and Corresponding Percent 260
Removals as Plotted in Figure 50
92 Data on F/M Ratios and Corresponding Effluent 261
Qualities as Plotted in Figure 51
93 Data on Sludge Age and Corresponding Effluent 262
Qualities as Plotted in Figure 52
94 Design Assumptions Utilized in Development of 264
UNOX System Costs
95 UNOX Facility: Estimated Construction Costs - 262
1976
96 UNOX System: Estimated O&M Costs - 1976 266
97 Characterization of 40-Acre Wastewater and Effluent 271
Loading in kg/day for the Sampling Period
98 40-Acre Facility Organic and Biological Samples 273
Locations and Identification Designations *
99 Results of GC Analysis of Combined Extracts of 274
Base/Neutral and Acid Fractions Isolated for
40-Acre Samples
100 Results of GC/MS Analysis of 40Acre Sludge Sample: 276
40A-ORG-COMP-7
101 Results of GC and GC/MS Analysis of 40-Acre 278
Sediment Samples
xv T
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TABLES (continued)
Number
102 Characterization of Washburn Tunnel Wastewater 283
and Effluent Loading in kg/day for Sampling Period
103 Washburn Tunnel Facility Organic and Biological 286
Sample Locations and Identification Designations
104 Results of GC Analysis of Combined Extracts of 288
Base/Neutral and Acid Fractions Isolated for
Washburn Tunnel Samples
105 Results of GC/MS Analysis of Washburn Tunnel 290
Sludge Samples WT-ORG-COMP-S1 6/1 7/27
106 Results of GC and GC/MS Analyses of Washburn Tunnel 291
Sediment Sample
107 Characterization of the Deep Shaft Wastewater and 296
Effluent Loading in kg/day for the Sampling Period
108 Deep Shaft Facility Organic and Biological Sample 298
Locations and Identification Designations
109 Results of GC and GC/MS Analyses of Deep Shaft 300
Composite Samples
110 Results of GC and GC/MS Analyses of Deep Shaft Grab 302
Samples
111 Specific Design, Performance and Economic Criteria 308
for Comparing Biodegradation Technologies
112 Cost of Equalization Facilities 317
B-l Potential Petrochemical Waste Products 344
B-2 Candidate Organic Toxic Constituents for Field 345
Sampling and Laboratory Analysis
B-3 General Classes of Organic Toxins for Analysis 346
in Field Samples
B-4 Final List of Constituents for Analysis at the 347
Four Field Sites
B-5 List of Organics Analyzed by GC/MS 348
xvn
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ACKNOWLEDGEMENTS
This document is the result of an extensive data base evalu-
ation and field sampling and analyses which included research and
development finds from industry, universities, EPA, and other
state and federal agencies. The guidance and assistance of
Mr. Charles J. Rogers, Project Officer, Solid and Hazardous Waste
Research Division, Municipal Environmental Research Laboratory of
the U.S. Environmental Protection Agency, Cincinnati, Ohio, is
gratefully acknowledged.
The individuals in the R&D community who contributed time
and effort to the project are too numerous to mention. Major
contributors to the project are listed below:
• Messrs. Welford S. Hutton and Jack Neeld
Gulf Coast Waste Disposal Authority
Houston, Texas
• Messrs. Don Sandford and Tom Gallo
Eco-Research, Ltd.
Calgary, Alberta, Canada
• Mr. R. M. Roberts
Analytical Research Laboratories, Inc.
Monrovia, California
• Mr. Mike Davidson and Dr. Juhee Kim
California State University
Microbiology Department
Long Beach, California
SCS project participants were Curtis J. Schmidt, Project
Director; Warren G. Hansen, Project Manager; and Mark S#. Mont-
gomery, Project Engineer. Technical support 'was provided by
Tom Dong, Craig Eaker, and Dr. Michael Swayne. Dr. Donald
Shilesky reviewed much of the technical information.
xvm
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SECTION I
INTRODUCTION
Organic constituents in aqueous process effluents from
numerous types of industries often include toxic or hazardous
compounds not readily removed by conventional biological treat-
ment processes. The same characteristics which make these
materials undesirable in plant discharges to receiving waters
may also adversely affect the in-plant biota, resulting in
reduced plant efficiencies. Nevertheless, biological treatment
is an important means by which such compounds can be economically
converted to less innocuous materials. For this reason, research
was conducted to identify and characterize types of treatment
processes or innovative treatment accessories and operational
methods which are successfully handling problematic organic
industrial wastes.
Section 212 of the Resource Recovery Act of 1970 (PL 91-512)
required the U.S. Environmental Protection Agency (EPA) to set
the groundwork for a comprehensive system of national disposal
sites for elimination of hazardous wastes. In 1974, work
describing the magnitude of the disposal problem and technology
descriptions was completed. From the resulting reports, it
became evident that treatment/disposal technology was inade-
quate. The Office of Solid Waste Management Programs (OSWMP)
asked that the Solid and Hazardous Waste Research Laboratory
(SHWRL) of the National Environmental Research Center, Cincinnati,
Ohio, conduct further in-depth assessments of various disposal
options. This report is the result of the study commissioned to
ascertain existing and promising biological detoxification and
disposal technologies.
The terms "hazardous waste" and "toxic waste" are used in
this study according to the scope of investigation and the
professional judgment of SCS Engineers. The definitions
developed for use in this report do not necessarily reflect EPA
definitions, and they may or may not be in agreement with uses
in federal legislation or private industry. This study is
purposely focused upon waste materials potentially biocidal,
carcinogenic, mutagenic, or bioaccumulative. Materials may,
therefore, be excluded which present explosion or corrosion
hazards in bulk, but are not considered biologically active as
described by the Federal Registry of Toxic Effects of Chemical
Substances.
1
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During the execution of this study, emphasis was placed upon
biological treatment technologies which are:
• Treating a wide range of classes of synthetic
or toxic organic compounds
• Processing toxic compounds without resulting
synergenic reactions and biological metabolites
which would present an equal or enhanced
potential for adverse environmental impact
• Being utilized on a large-pilot or full-scale
basis. Technologies which were demonstrated on
a bench scale only are not reported, except where
the process showed exceptional promise for
future development.
• Minimizing operating and environmental costs.
The system must be cost-effective and free of
secondary problems such as air pollution or
excessive sludge handling/disposal requirements.
The work reported herein proceeded in consecutive steps.
Initially, a data base and literature search was conducted to
describe the present treatment problem and prepare an inventory
of types and locations of innovative biological treatment
technologies presently developed and in use. The results of
this effort comprise Section III of this report. After informa-
tion was assembled on candidate study sites, four (4) locations
were selected for in-depth analysis. These sites included a
large-scale activated sludge plant, lagoon system, a Deep Shaft
pilot facility, and a UNOX pure oxygen plant. Three of the
plants are treating industrial effluents exclusively; the Deep
Shaft facility processes a 70:30 industrial/municipal raw
influent. The plants were selected to represent the following
specific process units or operational methodologies which
enhance biodegradation processes:
Intensi ve Aerati on. Use of aeration technology to
promote a high level of dissolved oxygen in the waste
flow, resulting in higher rates of chemical and
biologicaloxidation. «
Nutrient Addition. Industrial wastes are often
"unbalanced" in the nutritional requirements of
microorganisms. Addition of nitrogen and/or
phosphorus, for example, has been effective in
increasing biodegradation rates.
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Biological Seeding. The application of known species
to provide a seed for microbial populations has been
made easier through the development of especially
manufactured dried bacterial cultures. Species of
bacteria can be selectively produced which demonstrate
high rates of degradation for the particular waste
involved.
Substrate Alteration. Chemical pretreatment of wastes
prior to introduction into biological waste treatment
systems can be a valuable means of promoting rapid
biodegradation. This technique would be particularly
important in the neutralization of toxins.
Growth Phase Manipulation. Innovative sludge recycling
and clarification techniques may be used to optimize
the food-to-microorganism ratio and maximize the
metabolism rates.
Temperature Control. Biochemical reactions are
temperature-dependent. Higher rates of metabolism
have been associated with higher temperatures.
Techniques which use temperature control for enhancing
metabolism were studied.
Deep-Shaft Aeration. Oxygen transfer system comprised
of a 90- to 245-m (300- to 600-ft) shaft vertically
partitioned into downflow and upflow sections. Increased
pressure with depth coupled with air injection allows
increased oxygen transfer efficiencies to the point
where biodegradabi1ity of the substrate is considered
the limiting factor.
During the execution of the site studies, the field team
was charged with gathering information and making observations
concerning the following major topics:
• The types of wastes that are and are not physically
or chemically amenable to treatment through bio-
degradation .
• Process design and influence of waste characteristics
on the biological assimilative capacity at each
site studied.
• The impact of any process effluents upon the
indigenous biota when data is available.
• Efficiencies and costs incurred by site owners
utilizing biodegradation techniques and future
economics of the technology.
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t Potential for site design changes at existing
site facilities which will utilize and encourage
accelerated biodegradation of industrial and
hazardous organic wastes.
The results of these field investigations are reported in
Section IV.
During the execution of the initial field studies, it
became apparent to the contractor that insufficient data existed
in treatment plant files and elsewhere to properly describe the
presence and fate of specific organic constituents of interest.
As expected, different quantities and types of information were
available at each of the four plants. Gross measurements of
organic materials such as the Chemical Oxygen Demand (COD),
Biochemical Oxygen Demand (BOD), and Total Organic Carbon (TOC)
tests are of little value in situations where an evaluation of
specific problematic compounds is required. For these reasons,
chemical and biological sampling was instituted at three sites.
A detailed sampling plan was prepared to characterize the inputs
and outputs of specific organic toxins using gas/liquid chroma-
tography and mass spectrometry. Biological samplings were also
obtained to determine the characteristics of in-plant biota.
The results of this work are presented in Section V.
Section VI of this report utilizes the information assembled
in the previous sections to establish an engineering and economic
comparison of biological treatment technologies for organic
industrial process effluents. The goal of this exercise is to
guide the EPA and U.S. industries in selecting treatment processes
and comparing biological systems with chemical or physical/chemical
treatment approaches. Comparative criteria include overall
efficiency, operational and maintenance costs, capital and
construction costs, ability to treat a wide spectrum of classes
of organic compounds, susceptibility to shock loading or climato-
logical fluctuations, and minimization of adverse environmental
impact.
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SECTION II
CONCLUSIONS AND RECOMMENDATIONS
Conclusions and recommendations based on the field obser-
vations and analytical results, as well as background information
gathered during the extensive literature review, are presented
here in association with the project goals discussed in the
fol1owi ng secti ons.
The first goal involved the evaluation of treatment capa-
bilities of biodegradation as applied to problematic wastes. The
following was noted:
• The advantage of biological treatment schemes lies
primarily in the degree to which such systems are
acclimated to removing residual dissolved or colloidal
organic contaminants.
• Treatability of general classes or organic constituents
varies greatly and depends upon the biological system
applied. For example, in short retention/high aeration
systems recalcitrant materials may be removed by
stripping into the air. In systems retaining large
amounts of solids, in-plant digestion may result in
the release of metabolites into the effluent wastestreams
• Biological treatment is a significant technique for
permanently mineralizing materials that are moderately
biodegradable. Broad applications must be limited to
situations where shock loading is controlled, certain
extremely biocidal constituents are avoided, retention
time is high, influents are completely mixed, and
concentrated wastes are diluted.
The second goal involved the identification and description
of specific wastes being successfully or unsuccessfully treated.
The following was noted:
t Treatment of 35 organic compounds by a large series
lagoon system resulted in a significant reduction
of all compounds except fluorene, which was found to be
resistant to biodegradation. Phenols, cresols, and
polycyclic aromatic hydrocarbons were present in
high levels in sludges compared to influent-effluent
concentrations. This was attributed to the accumulation
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of these materials as metabolites of polymers and
other complex materials in sludges.
t An evaluation of degradation of 35 organic compounds
by a large, activated sludge system treating industrial
wastes indicated that phenol, 1,2-diphenyl-hydrazine ,
and benzidine were resistant to degradation. Phenol
was present in the influent with a concentration of
43 ug/1- Both aliphatic hydrocarbons and monocyclic
aromatics were detected in high concentrations (2
to 5 mg/1) in the waste sludges in relation to other
sludges examined.
• Biodegradability of textile chemicals indicated that
most materials were only marginally amenable to
conventional biological treatment and degrade very
slowly. Most dyes showed little change during 5-day
BOD tests, and there was little color change after
30 days. Under certain conditions, sulfur compounds
were reduced to sulfides or anaerobica1ly metabolized
to form thiols by bacteria in waste treatment systems,
resulting in odor problems. Some problematic organic
chemicals, such as low molecular weight acids and
alcohols difficult to degrade aerobically, degrade
anaerobically. The blending of domestic sewage with
industrial wastes can result in an improved nutrient
balance and provide for concentrated industrial
wastes dilution.
The third goal involved observation of any relationships
between wastes and indigenous plant biota (toxic or beneficial).
The following was noted:
• The flora of industrial waste treatment systems was
found to have qualities and quantities similar to
domestic wastewater treatment systems flora.
t During warmer months or under warm-waste conditions,
biological systems may be plagued by thermophilic
bacteria. Such populations are unstable and can
occasionally cause poor settling in secondary
clarifiers. *
• Nutrient concentrations in the recycled and wasted
sludges of treatment facilities should be evaluated
along with influent-effluent concentrations to provide
a complete picture of the balance of such materials in
relation to carbonaceous substrates. At the plants
studied, nutrient additions are based on the detection
of trace amounts in the aqueous plant effluents. Reduction
in costs for chemicals may be achieved by monitoring
nutrients in secondary sludge.
-------
were
The fourth goal involved an estimation of the time required
to effect efficient decomposition of the organic materials. The
following was noted:
• Based on the observations reported herein, the
biodegradation of problematic, or hazardous
organics requires a longer retention period in
a biological system than required for the reduction
of the Biological Oxygen Demand (BOD). Series
lagoon systems are the only waste treatment
option providing prolonged retention periods
(>1 day) necessary for stabilization of
recalcitrant organics.
The fifth goal involved an evaluation of organic wastes in
treatment facility effluents, including waste accumulations in
Sludges. The following was noted:
• The majority of organic compounds evaluated we
present in the waste streams in the parts-per-
billion range of concentration. Concentration
were below toxic or inhibitory levels, a key
factor in efficient biological assimilation of
wastes.
• Marginally degradable organics may be removed by
biological systems if the mixed liquor suspended
solids are maintained sufficiently high. Under
such conditions, compounds have been observed to
adsorb onto the biological solids and are removed
by subsequent clarification. Some of these
compounds can generate secondary sludge disposal
problems.
• Sludges and the sediments of receiving waters
appear to be sinks for the same types of organic
compounds observed in waste stream.
The sixth goal involved conducting engineering and economic
comparisons and evaluations of studied technologies. The
following was noted:
• Series lagoon systems can provide high system
flexibility, e.g., a variant of options for
waste flow patterns. Techniques for returning
settled biomass to aerated stabilization lagoons
should be considered for series lagoon systems
to include advantages of activated sludge systems.
• Additional development of pretreatment methods for
reducing the impact of varying waste stream char-
acteristics (toxic or inhibitory effects) on
-------
biological treatment can be applied more widely
to industrial wastes.
§ Biological seeding is only advisable under special
waste conditions. Continuous seeding must be
conducted to maintain a viable degrading population
where adverse environmental conditions, other
microbial predators, or excessive washout occurs.
The cost of continuous additions of large volumes
under such circumstances may be noncompetitive with
alternative treatment methods. An effective
alternative to seeding involves allowing for
acclimation to low concentrations of a waste before
increasing loadings.
$ In certain cases, activated carbon addition can be a
useful and cost-effective method of improving the
efficiency of existing industrial waste treatment
facilities. The effectiveness of the technique is
primarily due to surface-concentrating effects in
systems of dilute waste concentrations. The carbon
can also adsorb toxins, thereby reducing their
concentrations to levels where they are not bio-
logically inhibiting. Additional research efforts
should concentrate on effective techniques for
regenerating the spent carbon.
® Additional research and development should encourage
practical applications of optimal feedback control
systems in industrial waste treatment plants. Auto-
mation of critical operational steps can improve
the response to fluctuating influent characteristics.
© The fundamental objectives of innovative biological
treatment usually involve:
- Enhanced contact between wastes and microbial cells
- Enhanced oxygen transfer to the microbial cells
- Minimization of toxic effects.
Additional research is necessary to develop ways of enhancing
contact between wastes and microbial cells without generating
demand for additional treatment unit volumes, and also for the
fo1 lowing:
9 To ease the burden on biological treatment, raw
process discharges should be segregated for
possible chemical recovery, incineration,
stabilization, and other processing options.
-------
• Automated systems should be provided to divert
hydraulic or organic overloadings to spill basins.
• Proper pretreatment, the use of surge tanks or
lagoons, and process control and housekeeping at
source plants can have a significant impact on
treatment plant stability. The inclusion of surge
capacity can reduce the problem of solids overflow
from primary and secondary clarifiers.
• Criteria based on design, performance, and economic
considerations were defined and evaluated to select
series lagoon systems as the most robust technology
for application to general classes of industrial
wastes. Both pure oxygen and deep shaft systems
were judged to be superior from a design stand-
point. Series lagoons were judged to have the
best performance, and were also judged favorably
based on economic considerations.
• Deep Shaft technology has been found to be average
or better than average according to all cost criteria
except where construction costs and cost per unit of
waste removed are concerned. The higher removal costs
are based upon limited information about the application
of the new technology, and it is anticipated that future
industrial installations will prove the technology to
be extremely competitive. Removal costs expressed as
dollars per kg of BOD for other technologies were $0.11
for series lagoons, $0.55 for the UNOX systems, and
$0.22 for the activated sludge facility.
-------
SECTION III
LITERATURE REVIEW
THE WASTE STREAM
The production and discharge of industrial and hazardous
wastes have increased substantially during the last six decades.
The growth of major industrial centers in the United States has
been paralleled by increases in volume production of organic
solids in refinery and other chemical plant effluents. Each year
1.8 x 109 t (2.0 x 109 tons) of hazardous materials and 9.07 x
107 t (1-0 x 108 tons) of organic and inorganic waste by-products
are produced by U.S. industries. About 10 percent, or 9.1 x 106t
(1.0 x 107 tons) of this annual waste load is nonradioacti ve,
organic and inorganic hazardous materials (25). Based upon
approximate waste production rate, roughly 5 percent of overall
production, the petrochemical industry alone produces approximately
3.5 x 106 t/yr (3.9 x 106 tons/yr) of organic and inorganic
hazardous wastes, approximately 2.1 x 10" t (2.3 x 10° tons)
organic.
Waste streams composed primarily of organic constituents are
candidates for biological treatment. As shown in Figure 1,
organic-rich wastes can originate from five major industries. The
petroleum refining and organic chemical and synthetics industries
are both dependent upon various sources or derivatives of
domestic or imported crude oils. The third industry depends
upon cellulose resources and the milling of pulp and fiber into
wood and paper products. Products of the fourth industry (coal
conversion and steel milling) include gases, oils, and coke for
use in coke and steel production. Textile processing is the
fifth industry.
The quantity of hazardous organic constituents in tlje waste
streams from these and other U.S. industries represents about
60 percent of the total hazardous waste loading (25). Based on an
estimate of 9.1 x 106 t/yr (1.0 x 107 tons/yr), the organic com-
ponents then represent 5.4 x 1O6 t/yr (6.0 x 10^ tons/yr).
Growth of the wood, coal, and petrochemical industries and
modifications in production techniques have caused changes in the
amounts of wastes generated. These fluctuations, coupled with
simultaneous changes in the availability of raw materials, waste
product reuse, and consumer demand, make it difficult to predict
trends in effluent qualities. Total tonnage of product or waste
production for one industry may be low in comparison to
10
-------
CELLULOSE RESOURCES
CRUDE DOMESTIC OILS
SUBSTITUTED
ORGANIC
COMPOUNDS
,02 x 10 t/YR PHENOL
RAW PRODUCTS
UNSATURATEO HYDROCARBONS
GASOLINES. FUELS,
NIC ^^ INORGANIC
t/YR .22 X 10* t/YR
4.0 X 10 t/YR AHI1ONI A
2.0 X I02 t/YR CYANIDE
5.0 X 1O t/YR THIOCYANIOE
30 t/YR SULF1OE
2.1 X I05 t/YRCHLORIDE
SYNTHETIC RUDDER
PLASTICS I RESINS
SYNTHET1C F IBER5
ORGAN 1C \^__^^/ INORGANIC
t/YR 1.* X 10* t
SOLVENTS
DYES
SURFRACTANTS
I ORGANIC FIBER
CONVERSION
TO SETTLED
SOLIOS/BIOMASS
LAND DISPOSAL,
DIRECT DISCHARGE
EFFLUENT
DISCHARGE
Figure 1. Sources of organic and inorganic waste streams from various industries
-------
other organic material processors, but the amount
constituents emanating from certain processes, e.<
pesticide industry, may be relatively high.
of
hazardous
the
The following groups of waste-related parameters were cited
in the EPA Handbook for Monitoring Industrial Hastewater (8).
The parameters cited for each industry are those for which
effluent limitations are set on a general and individual basis.
The organic chemical and synthetics industries are considered
together in this review because of the similar effluent
consti tuents.
Petroleum Refining Industry
Ammonia
BOD5
Chloride
Chromium
COD
Color
Copper
Cyanide
Iron
Lead
Mercaptans
Nitrogen
Odor
Oil, total
PH
Phenol
Phosphorus, total
Sulfate
Sulfide
Suspended solids
Temperature
TOC
Total dissolved solids
Toxicity
Turbidi ty
Volatile suspended solids
Zinc
Steel Industry
Pulp and Paper Industry
total and fecal
Ammonia
BOD5
COD
Coliforms
Color
Heavy metals
Nutrients (nitrogen and
phosphorus)
Oil and grease
pH
Phenols
Sulfite
TOC
Total dissolved
Total suspended
Toxic materials
Turbidi ty
sol ids
solids
Ammonia
Chloride
Chromium
Cyanide
Iron
Oil and grease
PH
Phenol
Sulfate
Suspended
solids
Temperature
Tin
Zinc
Textile Mill Products Industry
Alkalinity
BOD5
Chromi urn
COD
Color
Heavy metals
Oil and grease
pH
Phenolics
S u 1 f i d e s
Suspended solids
Temperature
Total dissolved solids
Toxic materials
12
-------
Organic Chemicals and Synthetics Industry
BOD5
Chlorinated benzenoids and PNA's
Chloride, organic
COD
Cyanides
Heavy metals
Nitrogen, total
Oil, free-floating
PH
Phenol
Phosphorus, total
Other pollutants
Total dissolved solids
Total suspended solids
Sulphates, mercaptans
TOC
Zinc
Petroleum Refining
In the 1iterature, aqueous effluents from petroleum refineries
are not always well differentiated from solid waste components.
Treatment options will vary depending upon the percent water.
Table 1 (136) shows the quantities of potentially hazardous waste
and hazardous constituents generated each year by the United States
petroleum refining industry. In addition to the trace elements
shown, the oil and phenol fractions may be further differentiated
into polynuclear aromatics, specific phenolic compounds, and
various substituted and nonsubstituted hydrocarbons. These
materials form the major portion of those refining waste compounds
believed to be carcinogenic. Hydrocarbons may be introduced into
aqueous process streams in primary distillation processes, where
the crude feed stocks are entering the system. The three types
of saturated hydrocarbons- aliphatics, aromatics, and cyclic
aliphatics that may be found, differ in volatility and amenability
to biological degradation. Unsaturated hydrocarbons include the
olefinic series (alkenes). These compounds are more soluble
and reactive than saturated hydrocarbons and reactive in the plant
process and waste streams. Mixed aliphatic-aromatic compounds
can also be expected in petroleum refinery effluents (50).
Organic Chemicals and Synthetics
The petrochemical industry uses petroleum components for the
manufacturing of polymers, fibers, or complex organics resulting
from chemical synthesis. Specific industries specialize in
synthetic rubber, plastics and resins, synthetic fibers (nylon,
etc.), surface-active agents (dispersants , soaps), pesticides,
and other miscellaneous petroleum-derived products. It is
estimated that the total petroleum-based production yields 6.93 x
107 t/yr (7.6 x 107 tons/yr) (50).
13
-------
TABLE 1. QUANTITY OF POTENTIALLY HAZARDOUS WASTE AND
HAZARDOUS CONSTITUENTS GENERATED BY THE
PETROLEUM REFINING INDUSTRY (t/yr - 1974) (136)
Wfit
Total potentially hazardous wastes ^ •-
Total hazardous constituents (dry basis)
Phenol
CN
Se
As
Hg
Be
V
Cr
Co
Ni
Cu
Zn
Ag
Cd
Pb
Mo
NH4
PNA
F
Oil
1756633.3206
624540.9959
110884.7286
5.3367
1.07532
1.50562
2.07518
.44461
.07633
19.8619
87.782
2.7087
23.4657
22.0568
78.177
.52749
.19363
14.5644
2.1343
4.9334
.1126
811.93
109,80§
14
-------
The organic waste-stream components of organic chemical
and synthetic processing are extremely complex. Substitution and
synthesis reactions involving first-generation petroleum products
are supplemented or catalyzed by a variety of metals, halogens,
nonpetroleum-based organics, and intermediate substituted
chemicals. Complex catalysts are also used for enhancing such
reactions. In spite of the great variety of compounds manufactured
only 100 chemical products represent 90 percent of the total sales
of organic chemical intermediates (144).
The first generation petroleum products are the alkanes,
alkenes, aromatics, olefins, and paraffins, which are derived from
initial refining of crude petroleums (Figure 2). Intermediate
substituted organics are derived from chemical oxydation,
substitution or addition reactions of first generation products
with other organic or inorganic chemicals. These reactions form
ethylene oxide, carboxylic acids, and various organic acids.
Chemicals classified as organic intermediates may be market
products or temporary synthesis steps in the production of final
products such as synthetic detergent bases, plastics and resins,
fibers, or solvents (107).
Figure 2 shows the types of organic compounds that may be
present in waste streams of petrochemical product manufacturers.
As indicated, practically every organic intermediate product may
appear. However, the concentrations of each constituent in the
waste stream will vary, depending upon solubility, volatility,
and proximity to spills or contaminating process streams.
Additional factors affecting the concentration of organic chemicals
in aqueous petrochemical wastes include the age and condition of
reaction vessels and transfer piping, in-plant maintenance and
spill prevention, and the efficiency of energy and mass transfers
during the chemical reaction. Table 2 shows BOD and COD values
for a number of chemical industries. Note the high level of
COD compared to BOD.
The metal and nonmetal inorganic compounds in petrochemical
production waste streams can have significant impact upon bio-
logical treatment processes. Cyanide, chromium, and other trace
constituents can, at certain concentrations, inhibit metabolism
or severely disrupt cell membranes (88).
Metals appearing in process effluents are primarily unre-
covered catalytic materials, corrosion products, inorganic raw
material residues, and additives in association with the organic
waste residues (Figure 3). Processes such as catalytic reforming,
polymerization, alkylation, and dehydrogenation utilize metal
catalysts comprised of aluminum, molybdenum, iron, chromium,
or platinum (50). Other sources of metals include gas purification
(copper), cooling tower sludges, and cooling waters (zinc,
aluminum, and others). Zinc, chromium, or copper compounds Jare
also introduced into aqueous process streams to control corrosion
and prevent biological growth.
15
-------
(NAPMTHANES)
UNS4TURATED | 1 OUEFINS
HYDROCARBONS— —J I
MIXED ALIPHATIC- | ALKANES-AROMATICS—
•L— UNSAT. HYDROC-
AROMATICS
ORGANIC ACIDS | CARBOXYLlC ACIDS
AND SALTS ••••!
ALCOHOLS
ALDEHYDES AND r— ALKYL ALDEHYDES —
KETONES 1 I
ACCTONC
i
J
— 1 i — ETHYLENE i
I — 1 — PROPYLENE- — •-•
1 BUTYLENE
1 — TOLUENE 1
1 — XYLENE '
STYRENE
ORGANIC COMPOUNDS
1 — ACETIC 1
ESUCCINIC
CLUTARIC • '
ETHANOL,
PQOPANOL.
ISOPROPANDL
r — FORMALDEHYDE — — •
^
L— J — METHYL FORMATE
l^ISOPROPYL ETHER
L—PROPYLENE OXIDE
COMPOUND
POLYETHYLENE
PESCHLOROETHYLENE
FURFURAL — —
_i
ETHYL
CHLORIDE
CHLOROFORM,
CARBON TET.
VINYL,
CHLORIDE,
PROPYLENE
CHLORIDE
HEXACHLORIDE
I 1 OLAMINE
1 D I ETHANOL AM TNE-1
' — HEXAMETHYLENE —
DIAMINE
GANIC COMPOUNDS
QLOW SOLUBILITY
HIGH VOLATILITY
i MORE SOLUBLE THAN SAT.
I DEALKYLATION
PROCESS
-NYLON MANUFACTURE
1 OXIDATION AND PARAFFIN
OF CLEF I MS
i — SOLVENTS
— NYLON MANUFACTURE
EXTRACTION
CQNvFPsint ^pprttrr
' "" CALL
CRACKING OF PETROLEUM
SULFONATION "ROCESSES
*
-HIGH TEMP. TREATING PROCESSES
MANUFACTURE
COMPLEX OILS
Figure 2. Classification of
organic compounds which may
occur in petrochemical waste streams.
16
-------
TABLE 2. INDUSTRIAL WASTEWATER OXYGEN DEMAND AND ORGANIC CARBON (46)
Type of Waste
Chemical*
Chemical*
Chemical*
Chemical
Chemical
Chemical-refi nery
Petrochemical
Chemical
Chemical
Chemical
Chemical
Chemical
Chemical
Chemical
Nylon polymer
Petrochemical
Nylon polymer
Olefin processing
Butadiene processing
Chemical
Synthetic rubber
BOD5
(mg/£)
--
--
--
24,000
__
--
850
700
8,000
60,700
62,000
—
9,700
--
--
--
--
--
--
— —
COD
TOC
(mg/£) (mg/£)
4
2
2
41
3
1
1
17
78
143
165
15
23
112
350
,260
,440
,690
576
,300
580
,340
,900
,400
,500
,000
,000
,000
,000
,400
--
,600
321
359
,000
192
9
5
26
48
58
5
8
44
160
640
370
420
122
,500
160
900
580
450
,800
,000
,140
,000
,500
,800
--
,000
133
156
,000
110
BOD
2
1
1
1
2
1
1
:TOC
_ _
--
--
--
.53
--
--
.47
.55
.38
.34
.28
—
.76
--
—
--
--
--
—
—
COD:
6.
6.
6.
4.
4.
3.
3.
3.
3.
3.
3.
2.
2.
2.
2.
2.
2.
2.
2.
2.
1.
TOC
65
60
40
72
35
62
32
28
12
02
00
96
84
72
70
70
50
40
30
19
75
High concentration of sulfides and thiosulfates.
-------
-METALS
METALLIC
CATALYSTS
PT, Me, FE —r
Ni, Co, Cu —'
-CATALYTIC CRACKING
-CATALYTIC REFORMING
-DEHYDROGEMATION, ALKYLATION
-ISOMERIZATION, POLYMERIZATION
ANTI-CCRRCSION — i
BACTERICIDAL '
ACETATE SOL' N — 1
Cu CR
7N
r~
COOLER AND BOILER WATERS
EXTRACTION AND PURIFICATION OF BUTADIENE
REMOVAL OF CARBON MONOXIDE FROM
SYNTHESIS GAS PRIOR TO AMMONIA
SYNTHESIS
- NON-METALS
SODIUM
COMPOUNDS
SULFUR
COMPOUNDS
MlSCELLANEOUS•
-SODIUM HYDROXIDE
-SODIUM SULFATE
-SODIUM SULFITE'
-SODIUM SULFIDE—•
-SODIUM COMBINED WITH
PHENOL, CRESOL, SYLENOL
-SODIUM CHLORIDE .
SULFATES
-HYDROGEN SULFIDE •
MARCAPTANS
-SULFURIC ACID —
-SULFCNATES
-THIOPHENOLS
-SULFUR DIOXIDE-
r-CACL-
—CYANIDE -
•—PHOSPHATES AND•
.CHLORIDES
POLYPHOSPHATES
-PHOSPHORIC ACID —
-MAGNESIUM AND
CALCIUM SALTS
-POTASSIUM HYDROXIDE-
-AMMONIA (AMMONIA
SULFIDE)
-NITRIC ACID
-SPENT CAUSTIC STREAMS
-PHENOLIC SPENT CAUSTIC
-CRUDE OIL DESALTING
-CCNDENSATES AND SPENT CAUSTICS FROM
PRIMARY CONVERSION AND. REFINING
PROCESSES
-SPENT CAUSTIC FROM ALKYLATION SOLVENT
IN EXTRACTION
-SPENT CAUSTIC FROM AROMATIC SULFONATION
-CONDENSATES FROM CATALYTIC CRACKING
-GASES FROM COMBUSTION SOLVENT IN
AROMATIC EXTRACTION
•SPENT CAUSTIC PROM CAOH AS WASHING
AGENT (CHLORINATION)
•CONDENSATES FROM CATALYTIC CRACKING
-HYDROCYANATION REACTIONS
(NYLON MANUF.)
-CRUDE DESALTER EFFLUENTS AND SPENT
CAUSTIC STREAMS
-CORROSION CONTROL IN COOLING AND
BOILER WATER
-CATALYST IN POLYMERIZATION, ALKYLATION,
AND ISOMERIZATION
-WASTE SLUDGE FROM COOLING WATER
TREATMENT
-CAUSTIC WASH IN REFINERY OPERATIONS
-CONDENSATES FROM REFINERY PROCESSES
•AROMATIC NITRATION
Figure 3. Clarification of inorganic compounds which
may occur in petrochemical waste streams.
li
-------
Nonmetal constituents from petrochemical production include
salts, chlorides, cyanide, and phosphorous, nitrogenous and sulfur
compounds (Figure 3). Sodium salts, which may react chemically
with other inorganic or organic chemicals, originate primarily
from caustic wash streams. Sulfur compounds are important
because, in certain forms, they can be toxic to the receiving
biota or can generate odor problems. Hydrogen sulfide, thiols,
sulfates and sulfonates may be produced in extraction processes,
caustic washings, and catalytic cracking or conversion processes.
Under appropriate environmental conditions, sulfur compounds are
reduced to sulfides or anaerobically metabolized to form thiols
by bacteria in waste treatment systems. The generation of these
compounds can create severe operational and odor problems for
the treatment plant.
The Pharmaceuticals industry is a significant contributor of
organic hazardous wastes to the organic chemicals waste stream.
The types of waste and applied treatment methods require special
consideration because of the biocidal potential of some constit-
uents. In addition, certain pharmaceutical waste products may be
extremely resistant to biodegradation by conventional means.
An EPA contractor (6) has estimated that a total of 73,755 t
(81,300 tons) (wet basis) of hazardous wastes will be generated
by the Pharmaceuticals industry in 1977 (Table 3). Except for
225 t/yr (248 tons/yr) of heavy metal, most of these materials
are organic compounds. A summary of the typical organic
pharmaceutical hazardous waste materials to be found in process
effluents is shown in Table 4.
The largest tonnage of process wastes comes from the
production of antibiotics of fermentation. In the fermentation
industry, the antibiotics are produced as by-products of the
growth of molds and bacteria. During operations to recover the
antibiotics, the microorganisms are filtered off, usually with the
addition of an inorganic filter aid, such as diatomaceous earth.
This discarded product is termed "mycelium." The mycelium residue
is not considered hazardous, but may cause severe handling odor
problems if improperly disposed. Hazardous wastes generated during
antibiotic recovery include solvents and still bottoms.
The production of organic medicinal ingredients represents the
major source of hazardous wastes in the industry. Of the roughly
90,700 t (100,000 tons) of organic medicinals (excluding anti-
biotics) produced in the United States in 1973, only about 34,000
t (37,500 tons) were produced by the Pharmaceuticals industry
itself. The remainder was produced by suppliers closely allied
to the industry. Production of organic medicinals resulted in
wastes consisting of filter cakes, carbon, filter paper, sewage
process sludge, unrecoverable halogenated and nonhalogenated
solvents, and still bottoms (6).
19
-------
TABLE 3. HAZARDOUS WASTES GENERATED BY THE PHARMACEUTICAL INDUSTRY (6)
1977
Nonhazardous
Industry Segment
Medicinals from animal glands (8,000 t glands/yr)
Extracted animal tissue
Fats or oils
Filter cake (containing protein)
Aqueous solvent concentrate
Total medicinal s from animal glands
Total for production of active ingredients (SIC
SIC Code 2831: Biological Products
Aqueous ethanol waste from blood f ractionation
Antiviral vaccine
Other biologicals
Dry Basis
8,400
400
280
9,080
Code 2833) 193,000
--
--
Wet Basis*
8,400
. 400
560
9,360
1,285,000
--
--
Hazardous
Dry Basis
--
900
900
67,000
280
350
225
Wet Basis*
—
1,800
1,800
70,000
680
350
225
Total for biological products -- -- 855 1,255
SIC Code 2834: Pharmaceutical Preparations
Returned goods 11,300 11,300
Contaminated or decomposed active ingredient — _ 600 600
Totals for all industry segments : 204,300 1,836,300 70,445 73,755
Rounded to: 204,000 1,836,000 70,000 74,000
Wet weight estimates are given for all wastes in metric tons. The two wastes that typically have the
highest moisture content are biological sludge and mycelium from fermentations. Where the wet waste
estimates are the same as on the dray basis, the waste is usually disposed of with only a tninor amount
of moisture. However, disposal practices vary from plant to plant, depending on the form in which the
waste is produced.
-------
TABLE 4. SUMMARY OF TYPICAL TYPES OF ORGANIC PHARMACEUTICAL
HAZARDOUS WASTE MATERIALS (6)
Antibiotics (Penicillin, Tetracyclines, Cephalosporins)
Recovery Solvents Purification Solvents
Amyl acetate Butanol
Butanol Acetone
Butyl acetate Ethylene Glycol Monomethy! Ether
Methylisobutyl ketone
Alkaloids (Quinine, Reserpine, Vincristine)
Extraction Solvents Purification Solvents
Methanol Ethylene Dichloride
Acetone Naphtha
Ethanol Methylene Chloride
Chloroform Benzene
Heptane
Ethylene Dichloride
Crude Steroids
Still bottoms (Soybean Oil Residue)
Medicinals from Animal Organs (Insulin, Heparin)
Ethanol
Methanol
Acetone
Synthetic Organic Medicinals
Typical Solvents
• Acetone
Toluene
Xylene
Benzene
Isopropyl alcohol
Methanol
Ethylene Dichloride
Acetonitrile
Organic Residues (Still Bottoms, Sludges,
Polymers, Tars)
Terpenes
Steroids
Vitamins
Tranquilizers
Blood Plasma Fractions
Solvent
Ethanol
21
-------
As noted, biodegradabi1ity of various waste constituents is
the primary factor in determining amenability to biological treat-
ment methods. Struzeski (151, 152), in discussing various
nitroani1ines used in the production of sulfani1 amides , notes
that phenol mercury wastes are extremely resistant. Biodegrad-
ability testing was cited where the ortho- and meta-nitroani1ine
were found to be nondegradable. Additional problematic constit-
uents of significance in pharmaceutical wastes are the inorganic
constituents, specifically copper, lead, mercury, arsenic,
selenium, zinc, chromium, cyanides, and sulfides. The concen-
trations of some organic and inorganic constituents of drug
manufacturing waste are given by Patil et al . (121) and shown
in Table 5.
Pulp and Paper Milling
Pulp and paper mills are another source of aqueous hazardous
waste streams. Constituents to be expected in such effluents
include organic sulfur compounds, phenols, and a variety of oil
compounds. Zinc and mercury are also encountered; caustic
washing and process stream cooling contribute sodium and aluminum
compounds. Quantities of BODs per metric ton of product range
between 250 to 500 ppm; total solids are between 350 to 500 kg/t
(700 to 1000 kg/ton) of product, In addition, pulp and paper
mills can discharge small amounts of cellulose fibers. Such
materials are decomposed only by bacteria capable of producing
cellulases, enzymes capable of hydrolyzing the cellulose to
degradable sugars. Various plant proteins contain sulfur that is
converted to hydrogen sulfide during biological degradation.
Pulp processing results in the production of excess lignin, a
structural polymer. Lignin is a polymer of complex aromatic
alcohols and is relatively resistant to biological degradation.
In a survey of 74 bleached kraft mills, the medial mill was
found to have a production capacity of 454 t/day (500 tons/day);
average flow for such mills is 180 m3/day (48,000 gals/day).
These figures are used in calculating the effluent concentrations
shown in Figure 4. In the Development Document for Effluent
Limitation Guidelines for the industry (156), the EPA has indicated
that the following waste constituents should be controlled:
• BOD5
• Total suspended Solids (TSS)
• pH
• Color (not including groundwood, deinked and
nonintegrated subcategories)
• Ammonia nitrogen (ammonia base sulfite and ammonia
base dissolving sulfite only)
t Zinc (groundwood subcategories only)
22
-------
TABLE 5. DRUG MANUFACTURING WASTES (121)
Parameter
Calcium chloride
Sodium chloride
Ammon i urn su1 fate
Calcium sulfate
Sodium sulfate
Sulfanilic acid, etc.
Su1 fa drugs
P-Amino phenol, p-Nitrophenolate,
p-Nitrochlorobenzene
Amino-nitrozo ami no-benzene
Anti pyrene su1 fate
Analogous substances
Var. alcohols
Benzene, toluene
Chlorinated solvents
Concn. , mg/l
600 - 700
1,500 - 2,500
15,000 - 20,000
800 - 21,000
800 - 10,000
800 - 1,000
400 - 700
150 - 200
170
150
2,500
400
600
200
200
3,000
700
700
23
-------
PROCESS
WATER
WOOD YARD
PULP MILL
RECOVERY
AND
CAUSTICIZING
BLEACH PLANT
PAPER MILL
1.89 X 103 M^DAY
4,571 MG/L BOD5
18,285 MG/L TSS
34,285 MG/L COLOR
7.5 PH
11.35 X 103 M3/DAY
52,570 MG/L BOD5
38,856 MG/L TSS
148,568 MG/L COLOR
9.6 PH
9.46 X 103M^DAY
22,857 MG/L BODs
61,713 MG/L TSS
11,428 MG/L COLOR
8.4 PH
20. G2 X 10 M^'DAY
36,571 MG/L BOD5
20,571 MG/L TSS
148,568 MG/L COLOf?
2.0 PH
(ACID WASTE)
(ALKALINE WASTE)
15. 14 X 10
34,285 MG/L BOD5
11,418 MG/L TSS
331,421 MG/L COLOR
10.2 PH
15. 14 X 103 H3/DAY
27,428 MG/L BODg
77,713 MG/L TSS
11,428 MG/L COLOR.
7. 1 PH
RAW WASTE
73.82 X 10 M /DAY
178,282 riG/L BOD5
223,566 MG/L TSS
685,699 MG/L COLOR
Figure 4. Effluent characteristics: bleached kraft mill (156).
24
-------
Other parameters were considered, but were rejected because
of their unreliability in the surveyed data or their redundancy
in light of other testing.
In addition to the bleached kraft mills, there are other types
of pulping mills and paper production mills, including those
shown in Table 6.
Steel Making and Coal Gasification
A major industry using coal is the coke production industry.
Coke is required in the production of iron ore and other constit-
uents into steel. It is estimated that present U.S. coke
production for this industry is approximately 4.93 x 10? t/yr
(5.4 x 107 tons/yr) (11) and will increase in proportion to the
increasing steel production.
Gases resulting from the distillation of coal in coke
production are subjected to scrubbing and cooling processes to
remove contaminants prior to discharge to the atmosphere. In
by-product coke ovens, a large portion of the evolved gas is cycled
down and used for heating the distillation oven. Process gas
used in this manner must be stripped of contaminant hydrocarbons,
ammonia, sulfides, and cyanides, or the oven will become plugged
and corroded.
The cooling and scrubbing processes are the primary genera-
tion points for contaminated aqueous effluents. The most common
gas cleaning technology used in the United States is the semi-
direct system. Process effluents consist of steam condensate and
other wastes from the ammonia still and cooling tower effluents.
Excess ammoniacal liquor must also be wasted from the system.
These materials may be recovered for process reuse or for the
manufacturing of secondary products. However, synthesis of
competing products, such as anhydrous ammonia, has limited the
cost effectiveness of recovery and placed an increased demand
upon process effluent treatment facilities. Table 7 shows a
typical analysis of ammoniacal liquor and still waste.
Research of coke oven liquors subjected to treatment by
activated sludge processes was conducted for the British Coke
Research Association (91). A variety of liquors was described,
including limed and unlimed spent liquors and strong, medium, and
weak wastes. Data were presented showing the biologically
inhibiting constituents such as phenols, thiocyanate, sulfide,
chloride, and unknown compounds described in terms of an equivalent
permanganate value (Table 8)
The use of coal as an alternative energy source to petroleum
will increase substantially in the United States during the
remainder of this century. The primary coal conversion processes
25
-------
TABLE 6. 1972 PRODUCTION BY PULP TYPE AND
PAPER GRADES (156)
Pul p* 1 ,000 t (tons)
Special alpha & dissolving 1,521 (1,677)
Sulfite 1,931 (2,130)
Bleached kraft 12,672 (13,970)
Soda 127 (140)
Groundwood 4,188 (4,616)
Paper f
Newsprint 2,360 (2,600)
Tissue 3,106 (3,424)
Fine papers 9,087 (10,017)#
Coarse papers 10,310 (11 ,365)
*
U.S. Bureau of the Census data.
Grouping of American Paper Institute data.
§
Includes papers of textile fibers not subject to pulp
and paper guidelines.
26
-------
TABLE 7. TYPICAL ANALYSIS OF AMMONIACAL LIQUOR AND STILL WASTE (44)
ro
--j
Ammonia
Phenol
Cyanide
Thiocyanide
Sulfide
Chloride
Volume
Cfc/t)
Excess
ammoniacal
Cone.
(ppm)
3800
1500
20
600
2
7000
137.
*
liquor
Discharge
kg/102 t
coke
636.4
272.7
3.6
90.9
0.45
1136.4
7
Undephenolized still
waste
Discharge
Cone. kg/103 t
(ppm) coke
155 38.6
1320 363.6
—
—
—
4350 1119.1
229.5
Dephenolized stil
waste
1
Discharge
Cone. kg/103 t
(ppm) coke
110 25.0
158 35.5
—
__
__
5400 1468.2
187.8
Based on analysis of Armoo Sttel Corporation, Houston Coke Plant.
-------
TABLE 8. ANALYSES OF COKE OVEN LIQUORS BY THE BRITISH
COKE RESEARCH ASSOCIATION (7)
ro
CO
Liquor
A not limed
B not limed
B (synthetic)
C not limed
D not limed
E not limed
F not 1 imed
F not limed
Gl not limed
G2 not limed
G2 not limed
H limed
I limed
(H+I)1 limed
(H+I)2 limed
J limed
K not limed
Percent
of liquor
in influent
100
100
100
100
100
50
100
50
100
50
40
100
100
100
50
60
100
Loading.,
(kg/1000 itT
per day)
2005.0
1683.8
2711.0
1941.5
833.1
1923.8
1843.0
3018.2
1828.5
2824.0
2245.1
1090.8
1747.4
2199.2
1846.2
1076.7
900.2
Phenols
964
910
910
840
592
735
2231
1116
2335
1400
1120
530
910
592
296
345
Nil
Influent
analyses (mg/£)
CNS- $2032-
448
160
160
400
310
690
580
290
140
126
101
110
219
97-5
48-8
441
370
308
158
158
175
168
131
728
364
530
280
224
105
247
28
14
370
120
Cl-
3532
450
450
6410
888
2945
2041
1020
2135
968
774
2980
4690
1997
999
3089
49
Per-
manganate
value
2680
2260
2260
2600
1040
2400
5000
2500
4880
2340
1872
1460
2555
1335
668
1350
446
-------
planned for commercial scale implementation include gasification,
liquefaction, and the production of solvent-refined coal. It is
estimated that by 1990, approximately 1.42 x 108 m3/day of
synthetic natural gas (SNG) will be produced from coal by
approximately 20 standard-size SNG plants each producing 7.1 x
10° m3/day (84). If the United States moves to satisfy 20 percent
of the current U.S. oil consumption with coal derived synthetic
fuels, then approximately 90 of these plants will be required.
Jahnig and Bertrand (75) discuss the environmental effects
of coal gasification processes on water and air quality. Figure
5 shows the estimated process flow rates for a 7.1 x 10° m3/day
plant. The gas liquor flow is estimated at 14,500 t/day (16,000
tons/day) and includes the unreacted water or steam from gas-
ification and shift reactions, together with ammonia, phenols,
sulfur compounds, cyanides, and thiocyanates. Effluent from
waste treatment is estimated to be 4,934 t/day (5,439 tons/day),
or 98,682 t/day (109,114 tons/day), if 20 such plants were to be
constructed in the United States.
The condensate formed by cooling the raw gas contains water
from unreacted steam, together with oil, tar and contaminants
from coal decomposition. More of the latter are present in
gasification operations at relatively low temperature (926°C or
lower). The types of compounds present in this condensate or
sour water include sulfur compounds (sulfides, thiophene, etc.),
oxygen compounds (phenols, fatty acids, etc.), and nitrogen
compounds. Some 60 to 70 percent of the nitrogen in the coal feed
is ammonia; other nitrogen compounds are cyanides, amines, pyridine,
etc. Thiocyanates, ammonium polysulfides, etc. are a result of
the interaction of all these compounds. In general, the amounts
of contaminants are comparable to those in the water layer from
coal coking operations. In addition, sour water from gasification
may have a high content of fatty acids (75).
Textile Processing
Organic compounds commonly used by the textile industry
include dyes, surfactants, solvents, finishes, and synthetic
fibrous materials. Solvents are used as dye carriers while the
surfactants maintain the dye in a dispersed condition, maximizing
the fabric coloring processes. Synthetic or cotton and wool
fibers may occur in wash waters or spent dye charges. Textile
finishes are organic resins that are used to modify the appearance
and texture of the treated materials. Sizing agents such as poly-
vinyl alcohol (PVA) are also used.
Biodegradabi1ity studies of textile chemicals indicate that
most materials are only marginally amenable to conventional
biological treatment and degrade slowly (126). Most dyes show
little change during 5-day BOD tests, and there is little color
change after 30 days. Nevertheless, inert dyes may be removed by
29
-------
CO
o
VENT GAS
2,900
TO SULFUR
PLANT
2,250 INCLUDING CO2, VENT
400 H2S 12,700
1 10,900
COAL
FEED COAL
14,500 TION
t 1
AIR REFUSE
1,450 3,600
NITROGEN OXYGEN
14,050 4,260
t t
°2
PLANT
t
AIR
18,300
^ GASIFI- mm
"^ CATION ™"
t i
STEAM ASH
22,000 900
OXYGEN
4,300
TAIL
•^ SHIFT •—
t
STEAM
2,700
FLUE
GAS SULFUR GAS ASH
2,830 340
t t
N
PLANT
.t t
FEED AIR
2,270 900
29,750 180
t t
UTILITY
BOILER
t t
COAL AIR
2,720 27,200
•^ SCRUB — «•
|
GAS LIQUOR
14,500
AIR AND
MOISTURE
2,839,480
t
COOLING
TOWER
t
AIR
1,905,080
1 1 SNG
H250 MM
fFTL,flMo, SCFD
^"•""^
|
WATER
2,700
WATER TO
RE SF TREATED
o «„« *>r-r SLUDGE WATER
8.980 NET
1 36 38,100
NH3 * DISCHARGE » *
90 ^ 5,440 ^ ^
t 1 4 If
WASTE FRESH
WATER WATER
V V
GAS LIQUOR MAKE UP
14,500 38,140
Figure 5. Flow rates in coal gasification (t/yr) (75).
-------
biological systems if the mixed liquor suspended solids are
maintained sufficiently high. Under such conditions, dyes have
been observed to adsorb onto the biological solids and are removed
by subsequent clarification.
Aromatic solvents used by the textile industry can be
extremely problematic for biological treatment. Phenolic compounds
are especially toxic, and odor problems at plants attempting to
treat these compounds have been reported.
The biodegradation of textile dispersants, sizing agents, and
finishes depends upon the chemical compounds present in the
materials. Polyvinyl alcohol was found to be resistant to bio-
logical treatment when it contained acetate groups in the polymer.
The efficient hydrolysis of polyvinyl acetate yielding water-
soluble alcohol may result in a more readily degradable product.
However, the reduction of the polymer acetates may also make
stored products less resistant to decay (126). Some dispersants
are readily biodegradable, which may be attributable to the
emulsive properties. Finishing agents were found to have extremely
low BOD values compared to COD. This is attributed to the toxins
and metal catalysts used in the formulation of these petrochemical
products. Analyses of biological application for treatment of
textile wastes have been published and include detailed char-
acterizations of process waste streams. Waste streams in a
carpet-yard, fiber-dyeing facility in Rhode Island were analyzed
(134), and raw waste parameters and components were characterized
(Table 9). In this report, a relationship of COD to TOD (total
oxygen demand) concentrations was established where COD equalled
0.98 TOD, 2.51 BODs, and 2.54 TOC. However, these ratios are
only averages, and there is considerable fluctuation in the
sample data.
Evaluation of another full-scale textile plant in Rhode
Island (123) indicated that the presence of inorganic salts in
waste streams may result in corrosion and adversely impact
receiving waters. Dispersants and dye colors may also present
operational and discharge problems due to excessive foaming. Heat
in process wastes reduces oxygen solubility and adversely impacts
sensitive microbial populations in the receiving treatment plant.
Composite samples were collected. The variation in the composition
of plant discharges with time is shown in Figure 6. The negative
impact of such variations upon biological treatment plants can
be reduced with the use of surge tanks or equalization lagoons.
GENERAL WASTE QUALITIES
Many of the specific waste constituents and their associated
industrial process sources have been described. It may be
generally stated that wastewaters from the organic chemical
industries exhibit the following characteristics (107):
31
-------
TABLE 9. A RHODE ISLAND DYE-HOUSE RAW WASTE PROFILE AND
DYEING CYCLE COMPONENTS (134)
Color - units
(tinctorial strength)
PH
Temperature- C
BODej (biochemical
Avg.
2.5
4.3
43.3
inc
Range
0.7
4.0
32.2
QC
- 5.9
- 6.0
-51.1
7nn
COD (chemical oxygen
demand) mg/£ 700
Suspended Solids - mg/£ 27
Calcozine Acrylic Blue HP Cove
Calcozine Acrylic Red B
Dyes* Calcozine Acrylic Violet 3R
Calcozine Acrylic Yellow 3.RN
Astrazon Yellow 7GLL
Acetic Acid, 56%
Merpol DA
Retarder 98
Alizarine Light Blue 3F
Dyes Xylene Mill Green B
Melpol DA
Salt
Acetic Acid, 56%
Month Snub
Sulfuric Acid
Erioclarite B
Leveling Agent PD
Dye Omega Chrome Black ALA
Acetic Acid, 56%
Moth Snub
305 - 1450
6-70
Lanafast Orange RDL
Dyes Lanafast Navy NLF
Lanamid Red 2GL
Acetic Acid, 56%
Emkalana WSDC
Moth Snub
Dyes
Dyes
Astrazon Yellow 7GLL
Astrazon Red GTL
Astrazon Blue 5GL
Acetic Acid, 56%
Merpol DA
Retarder 98
Salt
Sevron Yellow 3RL
Astrazon Red GTL
Astrazon Blue 5GL
Nabor Blue 2G
Acetic Acid
Merpol DA
Salt
Components which develop co'Tor of the wastewater are designed above as "Dyes'
The other components are used for stabilization, leveling, pH control, etc.
32
-------
27000H
24000
21000-
18000-
w>15000-
e
o
12000-
c
o
o
c
o
U 9000-
6000-
300
COD
BOD
A.
Suspended ^
Solids
Time (Hours)
Figure 6. A Rhode Island textile industry effluent profile:
BOD, and suspended solids versus time (123).
COD,
33
-------
• High concentrations of COD, consisting of an array of
organic compounds with widely varying biological
degradability and adsorption characteristics.
t High total dissolved solids
• Small quantities of compounds inhibitory to
biological treatment
t Radical variations in waste characteristics as
product mix and production processes are altered
t Spills or emergency conditions that can stress or
destroy a biological treatment system's microbial
population through toxicity or corrosion
Heavy metals from the catalysts used.
The high level of materials exerting a chemical oxygen demand is
attributable in part to acid or caustic wash and steam condensates
Industrial cooling water may be contaminated by system leakage
or poor in-plant maintenance. It is common practice to mix cool-
ing water with concentrated organic by-products for dilution
prior to discharge.
Washing, scrubbing and crude petroleum desalting all
contribute dissolved solids to waste flows. Sodium hydroxide
solutions are frequently used in petrochemical processes and can
carry sulfur and phenolic compounds, and organic acids. Desalt-
ing of crude oils is an important operation in the refining
industry and can result in significant discharges of saline water.
The high salinity of such process effluents can have a significant
impact upon the types of biota that will be present in waste treat-
ment processes. The presence of heavy metals and ammonia nitrogen
can also substantially affect the treatment of industrial wastes.
The maximum tolerable concentrations of toxic materials in
biological waste treatment plants have been reported for many
materials. Occasionally, treatability studies have to be made
to determine the maximum allowable concentration of the toxic
substance in a biological treatment system. In general, the
threshold toxicity levels for biological treatment systems are
higher than the allowable standards for surface waters.. Establish-
ing maximum concentrations for toxins in biological treatment
plants is useful only if the quantities of toxins are reduced
during the treatment, as is the case with phenols. Often, it is
necessary to decrease the concentration of the toxic material by
pretreatment. However, it is necessary to guard against the so-
called synergistic effect of certain materials. One industry may
be allowed to discharge zinc below the toxic level, another
industry may be-allowed to do the same with copper. The resulting
combination of both discharges will have a synergistic effect and
may cause biological deterioration in the receiving stream or
the treatment plant.
34
-------
Ammonia nitrogen is present in many natural waters in
relatively low concentrations, while industrial streams often
contain exceedingly high concentrations of ammonia. Nitrogen in
excess of 1,600 mg/£ has proven to be inhibitory to many micro-
organisms present in the activated sludge basin. Sulfides are
present in many wastewaters either as a mixture of HS-H^S
(depending on pH), sulfonated organic compounds, or metallic
s u 1 f i d e s .
The influence of heavy metals on biological processes has
been the subject of many investigations. Toxic thresholds for
copper, zinc and cadmium have been established at approximately
1 mg/£.
There is a potential for the continuous introduction of
organic toxins and heavy metals in a manner that will signifi-
cantly affect the quality of the microbial populations in treat-
ment plants. Such materials may be trace constituents which may
play important roles in determining the in-plant kinetics of
bioconversion. There is always opportunity for accidental spills
or process breakdown which can result in the discharge of
concentrated "slugs" of marginally degradable organics or toxic
materials to the treatment system. When these types of waste
fluctuations occur, they can affect the treatment system in the
fol1owi ng ways :
• Reduction in the BOD and COD removal efficiencies
• Alteration of solids settling characteristics in
the primary or secondary clarifiers (increased
solids in plant effluents)
• Accumulation of odor generating compounds in
quiescent tanks or lagoons
• Clogging of biological trickling filters.
The seriousness of these conditions depends upon the extent to
which the microbial population has been altered and the quantity
of solids and toxic compounds that has accumulated in the system.
Very mild system upsets have been observed where new types of
organic compounds are introduced. In certain cases, after an
initial lag period, the microbial population will acclimate to the
new waste and begin assimilating the material. In contrast, the
introduction of concentrated wastes containing high levels of
toxins or corrosives may result in the system "souring". Inorganic
compounds present in organic chemical industry wastewaters include
a number of metal and nonmetal compounds. Trace metals may
interfere with the metabolic biochemistry of microorganisms.
Caustics and nonmetals can destroy cellular membranes and microbial
tissues.
35
-------
Chemical industrial wastes pose additional problems to
receiving treatment plants or environments. In petroleum refining
and pulp and petrochemical processing, some aqueous process streams
have been in direct or indirect contact with exothermal reactions
or heated vessels. The elevated temperature of these effluents
has a demonstrated impact upon the ecological composition of the
receiving environment. Waste temperatures in excess of 40°C will
tend to favor thermophilic microbial species. Populations of
these types of bacteria are not as resistant to process fluctua-
tions and may also inhibit the settling of biological floes during
secondary clarification. Nevertheless, mild increases in waste
temperatures may actually enhance biological metabolism in colder
climates; the optimum temperature is usually between 30 and 37°C.
Another important characteristic of organic industrial waste
streams is the relative imbalance of nutrient compounds. Petroleum
contaminants in such streams are products of raw feedstocks com-
prised chiefly of carbon compounds. The high concentrations of
these carbonaceous wastes in relation to any nitrogenous or
phosphorous compounds make them difficult to biologically degrade
in the receiving environment. It is generally stated that the
optimum carbon:nitrogen:phosphorus ratio is 100:10:1. Studies
of the microbial aspects of petroleum degradation agree that
nitrogen and phosphorus are the limiting elements in environmental
biodegradation of materials such as crude oil.
Significant enhancement of biological growth on oil (from 3
to 70 percent) with additions of nitrate and phosphate have been
reported (31). Nutrient addition may be accomplished by the
addition of chemicals such as ammonia and phosphoric acid or by
mixing nutrient-deficient wastes with nutrient-rich waste streams.
Ammonia-rich wastes, such as those from fertilizer manufacturing
plants, can be treated biologically (71) and may be mixed with
carbonaceous wastes. Ammonia may also be present in condensates
from refining or coking processes, and nitric acid is often
present in wastes discharged from aromatic nitration processing
(50). Phosphates and polyphosphates appearing in cooling and
boiler waters (where they are used for corrosion control) can
provide a phosphorus input to biological treatment. Phosphoric
acid is also used as a catalyst in polymerization, alkylation, and
isomerization processes and may appear in aqueous waste streams
from those processes (50).
In some industrial waste streams, certain nutrient compounds
may be present in excess. When such effluents are discharged
into lakes, ponds, and surface streams, the presence of nitrogen
and phosphorus is particularly undesirable, since it can enhance
eutrophication of the receiving waters. The chemical form in
which nutrients are present may differ and vary with the degree
of treatment. Nitrogen can be present as ammonia, nitrate,
nitrite, and organic nitrogen in the form of proteins, urea, and
amino acids. Phosphorus can be present as orthophosphates or
organic phosphorus (8).
36
-------
Nutrient assimilation and removal by biological treatment
processes is, therefore, an important factor in ensuring efficient
industrial waste treatment as well as protection of receiving
waters. Insoluble organic materials are present in most industrial
effluents, and concentrations of organic solvents, greases, or
oils that are immiscible in water will tend to partition in treat-
ment process units. Synthetic textile fibers, paper, cotton, and
resin column beads are also in this category.
The partitioning characteristics of organic liquids are
usually used to effect separation and treatment. Lighter-than-
water materials that are not removed by in-plant processes or
pretreatment can be treated at the receiving plant by using
skimmers (98) or API-type oil/water separators. If highly
volatile materials such as gasoline and ether are present, they
may be toxic and can generate odorous and explosive vapors.
Excessive quantities of such materials must be removed prior to
discharge to the biological treatment plant. Heavier-than-water
materials and other organic solids will usually be removed by
primary sedimentation units. Such materials are reported to be
low in nitrogen and phosphorus content, and nutrient deficiency
can result if primary removal is inefficient and loading to the
bioreactor is too high (98).
CLASSES OF ORGANIC WASTES NOT AMENABLE TO BIODEGRADATI ON
Most organic compounds are, to a greater or lesser extent,
biodegradable. Yet a variety of materials, because of their
toxic, complex, or inert nature, cannot be degraded by treatment
plant microbes during the conventional retention period. A
number of innovative operational and plant design approaches have
been suggested to enhance the biological degradation of these
organ i c s. These are the main topic of this report.
Nevertheless, there remain certain classes of compounds that
are extremely refractory and cannot be biologically treated. The
impact of such materials upon the treatment system is, of course,
dependent upon the concentration introduced and the contact period
with and species present in the microbial population. System
poisoning may be avoided by storing extremely toxic or concentrated
wastes in spill tanks or lagoons. The waste may then be mixed
with other influents at a low rate to ensure adequate dilution
in the bioreactor. However, such an approach may not be economi
cally feasible if the production volume of such wastes is large
and continuous.
The petrochemical industry is plagued by a number of compounds
which, when present in waste streams in concentrations above
certain limits, are a problem to biological treatment. A list of
identified problem concentrations for a number of materials is
shown in Table 10. Much information about the relative degrad-
ability of compounds has been derived through laboratory
manometric and batch culture studies (67).
37
-------
TABLE 10. PROBLEM CONCENTRATIONS OF TESTED MATERIALS AS DETERMINED
BY MANOMETRIC INVESTIGATIONS (67)
Problem Concentration (mg/f)
Chemical
n-Butanol
sec-Butanol
t-Butanol
Ally! alcohol
2-Ethyl-l-hexanol
Formaldehyde
Crotonaldehyde
Acrolein
Acetone
Methyl isobutyl ketone
Isophorone
Diethylamine
Ethylene diamine
Acrylonitrile
2-Methyl-5-ethylpyridine
N,N-dimethylaniline
phenol
Ethyl benzene
Sodium benzoate
Ethylene dichloride
Ethyl acrylate
Sodium acrylate
Dodecane
Dextrose
Ethyl acetate
Ethylene glycol
Diethylene glycol
Tetralin
Kerosene
Cobalt chloride
Substrate
Limiting
>1000
500-1000
^200
>1000
>1000
150-500
>1000
>1000
>1000
>1000
150-500
600-1000
>1000
>1000
>1000
>1000
>1000
Non-Substrate
Limiting
>1000
>1000
>1000
>1000
50-100
50-100
20-50
>1000
100-300
300-1000
100-300
100
100
300-1000
>300
300-600
>500
>1000
>900
>1000
>500
>1000
^Compound was arbitrarily classified as a problem when the activity ratio
was less than 0.5. The 0.5 level was considered to be a decrease of more
than 50 percent of the total gas production over that in the unfed
manometric control.
38
-------
Different organic compounds at the same concentration will
have varying impacts upon microbes with resultant levels of
biodegradabi1ity depending upon environmental and chemical
conditions. Numerous studies of the degradation of hydrocarbons
in marine and fresh-water environments indicate that diauxic
growth may be an important governing factor in determining
degradation of mixed food substrates (77). It is apparent that
some, but not all, organisms have a preference for peptones,
carbohydrates, and other forms of readily usable carbon sources
over hydrocarbons or synthetic organic compounds (77). The
sequential utilization of preferred substrates from a mixture has
also been demonstrated for various classes of hydrocarbon and
synthetic organic molecules. Investigators (77) have noted the
preference that bacterial mixed cultures have for n-alkane
molecules of light molecular weight. The following generalizations
may be drawn concerning diauxic growth in mixed industrial wastes:
• Non-aromatic or cyclic aromatic compounds are
preferred over aromatics.
• Materials with unsaturated bonds in their
molecules, e.g., alkenes, alkynes, tertiary
amines, etc., are preferred over materials
exhibiting saturated bonding.
0 The comparative stereochemistry of the molecules of
certain compounds makes them more or less susceptible
to attack by microbial enzymes. The n-isomers of the
lighter weight molecules are preferred over branched
isomers and complex, polymeric substances.
• Soluble organic compounds are usually more readily
degraded than insoluble materials. Biological
waste treatment is most efficient in removing
dissolved or colloidal materials whichare more
readily attached by enzymes and transported through
cell membranes. Readily dispersed compounds are
usually degraded more rapidly because of the increased
surface area that is presented to the individual micro-
organi sms .
• The presence of key functional groups at certain
locations in the molecules can make a compound more
or less amenable to biodegradation . Alcohols, for
example, are often more readily degraded than their
alkane or alkene homologues. On the other hand,
halogenation of certain hydrocarbons may make them
resistant to degradation.
39
-------
Reports of research on aerobic biological oxidation have
identified the following classes of wastes as generally resistant:
Oil
Isoprene
Methyl vinyl ketone
Morpholi ne
Ethers
Ethylene chlorohydrin
Polymeric compounds
Polypropylene benzene
Tertiary and volatile
Aromati cs
Alkyl-aryl groups
Tertiary aliphatic alcohols
Tertiary benzene sulfonates
Trichlorophenols
sulfonates
a 1 i p h a t i c s
Biodegradabi1ity in complex waste mixtures is not identical
to that in laboratory experiments. Some organic materials can
polymerize or react in a synergistic manner upon contact with
other wastes. Acclimation of microorganisms can also affect
biodegradabi1ity. The lack of sufficient acclimation of a
biological seed to the waste sample has probably been the major
source of contradictory data and misunderstanding of treatability
studies (50). Recent treatability studies have taken these
problems into account in attempting to utilize realistic activated
sludge specimens to degrade complex organic substrates.
Pitter (122) used activated sludge inocula adapted to various
test substrates to compare the biological degradabi1ity of a
number of organic compounds. Results of these experiments are
shown in Tables 11 through 13. The experiments were conducted
until there was no detectable decrease in COD. The total
percentage of COD removed and rate of degradation were evaluated.
Materials were considered readily biodegradable if 90 percent
or more of the initial COD was removed in 120 hr of incubation.
Only a low or zero removal of COD was achieved with refractory
compounds such as pyrogallol, metol and nitroani1ines .
Other treatability studies have determined the ratio of
BOD5 and COD of wastewater compounds (46). This ratio indicates
the fraction of dichromate-oxidizable materials which is amenable
to biological degradation. A high ratio, for example, would
indicate that many of the dissolved organic materials can be
degraded biologically, while a low value would indicate the
presence of a significant fraction of bioresistant organic
constituents. Table 14 shows the measured BOD and COD as a
percent of theoretical oxygen demand for several classe? of
chemicals. Note the relatively high degradabi1ity of most unsub-
stituted aliphatic compounds.
REQUIRED DEGREE OF TREATMENT
Amendments to Public Law 92-500 control the discharges of
hazardous industrial waste effluents. Foremost among these is the
National Pollutant Discharge Elimination System (NPDES), 33 U.S.C.
1251 (incorporated as Section 402), which establishes effluent
discharge limitations of waste constituents. Permits issued in
40
-------
TABLE 11. BIOLOGICAL DEGRADABILITY OF AROMATIC COMPOUNDS (122)
Compound
Aniline
Aminophenolsulphonic acid
Acetanilide
p-Ami noacetani 1 i de
o-Aminotoluene
m-Aminotoluene
p-Ami notoluene
o-Aminobenzoic acid
m-Aminobenzoic acid
p-Aminobenzoic acid
o-Aminophenol
m-Aminophenol
p-Ami nophenol
Benzenesulphonic acid
m-Benzenedisulphonic acid
Benzaldehyde
Benzoic acid
o-Cresol
m-Cresol
p-Cresol
D-Chloramphenicol
o-Chlorophenol
p-Chlorophenol
o-Chloroaniline
m-Chloroaniline
p-Chloroaniline
2-Chloro-4-nitrophenol
2,4-Dichlorophenol
1 ,3-Dinitrobenzene
1 ,4-Dinitrobenzene
2, 3-Dimethyl phenol
2,4-Dimethylphenol
3,4-Dimethylphenol
3, 5-Dimethyl phenol
2, 5-Dimethyl phenol
2,6-Dimethylphenol
3,4-Dimethylanil ine
2,3-Dimethylanil ine
2,5-Dimethylanil ine
2,4-Diaminophenol
2,5-Dinitrophenol
2,6-Dinitrophenol
2,4-Dinitrophenol
3,5-Dinitrobenzoic acid
3,5-Dinitrosalicylic acid
Furfuryl alcohol
Percent Removed
(based upon COD)
94.5
64.6
94.5
93.0
97.7
97.7
97.7
97.5
97.5
96.2
95.0
90.5
87.0
98.5
63.5
99.0
99.0
95.0
95.5
96.0
86.2
95.6
96.0
98.0
97.2
96.5
71.5
98.0
0
0
95.5
94.5
97.5
89.3
94.5
94.3
76.0
96.5
96.5
83.0
see
see
85.0
50.0
0
97.3
Rate of biodegradation
(mg COD g-' h'l)
19.0
7.1
14.7
11.3
15.1
30.0
20.0
27.1
7.0
12.5
21.1
10.6
16.7
10.6
3.4
119.0
88.5
54.0
55.0
55.0
3.3
25.0
11.0
16.7
6.2
5.7
5.3
10.5
--
--
35.0
28.2
13.4
11.1
10.6
9.0
30.0
12.7
3.6
12.0
note 1
note 1
6.0
--
--
41.0
41
-------
TABLE 11 (continued)
Compound
Furfuryl aldehyde
Gallic acid
Gentisic acid
p-Hydroxybenzoic acid
Hydroquinone
Isophthalic acid
Metol
Naphtoic acid
1-Naphthol
1-Naphthylamine
1-Naphthalenesulfonic acid
l-Naphthol-2-sulphonic acid
1 -Naphthyl ami ne- 6- sul phonic acid
2-Naphthol
p-Nitroacetophenone
Nitrobenzene
o-Nitrophenol
m-Nitrophenol
p-Nitrophenol
o-Nitroluene
m-Nitrotoluene
p-Nitrotoluene
o-Ni trobenzal dehyde
m-Nitrobenzal dehyde
p-Ni trobenza 1 dehyde
o-Nitrobenzoic acid
m-Nitrobenzoic acid
p-Nitrobenzoic acid
o-Nitroaniline (see note 2)
m-Nitroaniline (see note 2)
p-Nitroaniline (see note 2)
Phthalimide
Phthalic acid
Phenol
Phloroglucinol
N-Phenylanthranilic acid
o-Phenylendiamine (see note 3)
m-Phenylendiamine (see note 3)
p-Phenylendiamine (see note 3)
Pyrocatechol
Pyrogal lol
Resorcinol
Salicylic acid
Sulphosalicylic acid
Sulphanilic acid
Percent Removed
(based upon COD)
96.3
90.5
97.6
98.7
90.0
95.0
59.4
90.2
92.1
0
90.5
91.0
0
89.0
98.8
98.0
97.0
95.0
95.0
98.0
98.5
98.0
97.0
94.0
97.0
93.4
93.4
92.0
0
0
0
96.2
96.8
98.5
92.5
28.0
33.0
60.0
80.0
96.0
40.0
90.0
98.8
98.5
95.0
Rate of Biodegradation
(mg COD g'T h'1)
37.0
Ort f\
20.0
80.0
100.0
r M O
54.2
T J*" f\
76.0
0.8
15.5
38.4
18.0
18.0
39.2
5.2
14.0
14.0
17.5
17.5
32.5
21.0
32.5
13.8
10.0
13.8
20.0
7.0
19.7
--
—
--
20.8
78.4
80.0
22.1
•--
—
__
—
55.5
__
57.5
95.0
11.3
4.0
42
-------
TABLE 11 (continued)
Percent Removed Rate of Biodegradation
Compound (based upon COD) (mg COD g"T h"1)
Thymol 94.6 15.6
p-Toluenesulphonic acid 98.7 8.4
2,4,6-Trinitrophenol 0
Note 1. 2,5 and 2,6-dinitrophenol were at higher concentrations not
degraded. 2,6-Dinitrophenol was at lower concentrations decomposed
with long adapted activated sludge (40 days). 2,5-Dinitrophenol
was biochemically stable.
Note 2. The degradation of nitroanilines was determined photometrically in
the concentration range from 25 to 30 mg 1 .
Note 3. The degradation of phenylenediamines was determined photometrically
in the concentration range from 25 to 30 mg 1"'. p-Phenylenediamine
was comparatively well degradable.
43
-------
TABLE 12. BIOLOGICAL DEGRADABILITY OF
CYCLOALIPHATIC COMPOUNDS (122)
Percent Removed Rate of Biodearadation
Compound (based upon COD) (mg COD g~T h'1)
Borneol 90.3 8.9
Caprolactam 94.3 16.0
Cyclohexanol 96.0 28.0
Cyclopentanol 97.0 55.0
Cyclohexanone 96.0 30.0
Cyclopentanone 95.4 57.0
Cyclohexanolone 92.4 51.5
1,2-Cyclohexanediol 95.0 66.0
Dimethylcyclohexanol 92.3 21.6
4-Methylcyclohexanol 94.0 40.0
4-Methyleyclohexanone 96.7 62.5
Menthol 95.1 17.7
Tetrahydrofurfuryl alcohol 96.1 40.0
Tetrahydrophthalimide 0
Tetrahydrophthalic acid 0
44
-------
TABLE 13. BIOLOGICAL DEGRADABILITY OF
ALIPHATIC COMPOUNDS
Percent Removed Rate of Biodegradation
Compound (based upon COD) (mg COD g~' h~')
Ammonium oxalate 92.5 9.3
n-butanol 98.8 84.0
Sec. butanol 98.5 55.0
Tert. butanol 98.5 30.0
1,4-Butanediol 98.7 40.0
Diethylene glycol 95.0 13.7
Diethanolamine 97.0 19.5
Ethylene diamine 97.5 9.8
Ethylene glycol 96.8 41.7
Glycerol 98.7 85.0
Glucose 98.5 180.0
n-Propanol 98.8 71.0
Iso-Propanol 99.0 52.0
Triethylene glycol 97.7 27.5
45
-------
TABLE 14. COMPARISON OF COD, BOD, AND ThOD WITH
RESPECT TO THEORETICAL ORGANIC CHEMICALS (46)
Chemical Group
Aliphatics
Methanol
Ethanol
Ethyl ene glycol
Isopropanol
Maleic acid
Acetone
Methyl ethyl ketone
Ethyl acetate
Oxalic acid
Aroma tics
Toluene
Benzaldehyde
Benzoic acid
Hydroquinone
o-Cresol
Nitrogenous organics
Monoethanol ami ne
Acrylonitrile
Aniline
Refractory
Tertiary-butanol
Diethylene glycol
Pyridine
ThOD
(mg/mg)
1.50
2.08
1.26
2.39
0.83
2.20
2.44
1.82
0.18
3.13
2.42
1.96
1.89
2.52
2.49
3.17
3.18
2.59
1.51
3.13
Measured
COD
(mg/mg)
1.05
2.11
1.21
2.12
0.80
2.07
2.20
1.54
0.18
1.41
1.98
1.95
1.83
2.38
1.27
1.39
2.34
2.18
1.06
0.05
COD
ThOD
(%)
70
100
96
89
96
94
90
85
100
avg. 91
45
80
100
100
95
avg. 84
51
44
74
avg. 58
84
70
2
avg. 52
Measured
BOD 5
(mg/mg)
1.12
1.58
0.36
0.16
0.64
0.81
1.81
1.24
0.16
0.86
1.62
1.45
1.00
1.76
0.83
nil
1.42
0
0.15
0.06
*
BOD5
ThOD
(X)
75
76
29
7
77
37
74
68
89
avg. 56
28
67
74
53
70
avg. 58
34
0
44
avg. 26
0
10
2
avg. 4
46
-------
compliance with NPDES specify the limitations and monitoring
requirements that must be implemented in order to comply with
the Water Pollution Control Act. In addition, the permits may
specify details about responsibility for compliance between
treatment and joint industrial facilities that might contribute
waste streams to the former. To encourage maximization of
pollutant removal, the permits may further specify that industrial
waste stream sources provide monitoring of their effluents and
report such information to receiving treatment plants. The
permit also establishes daily average and daily maximum effluent
limitations for each waste stream source. The typical character-
istics measured in a petrochemical plant effluent are:
BOD5 Phenols Lead
COD R-Ci Arsenic
TSS Phosphorus TKN
Oil and grease Fluoride Flow
NH3-N Cyanide Temperature
Chromium Mercury pH
Sections 304, 306 and 307 of the Federal Water Pollution
Control Act Amendments of 1972 give the EPA the responsibility for
establishing effluent limitations guidelines for industrial
discharges.
Organic Chemicals Industry
The EPA contractor conducting the study to fulfill the
requirements of the above sections indicated four subcategories
of effluent limitations for different groups of organic chemicals
industries:
• Nonaqueous processes - Contact between water and
reactants or products is minimal. Water is not
required as reactant or diluent and is not formed
as a reaction product, but is only used for
periodic washes or catalyst hydration.
• Process with process water contact as steam diluent
or absorbent - Process water is in the form of
dilution steam, direct product quench, or absorbent
for effluent gases. Reactions are all vapor-phase over
solid catalysts. Most processes have an absorber
coupled with steam stripping of chemicals for
purification and recycle.
• Continuous liquid-phase reaction systems - Reactions
are liquid-phase, the catalyst in an aqueous medium.
Continuous regeneration of the catalyst requires
extensive water usage, and substantial removal of
spent inorganic by-products may be required. Additional
process water is involved in final purification or
neutralization of products.
47
-------
t Batch and semi-continuous processes - cleaning of
noncontiguous production equipment; most reactions
are liquid-phase with aqueous systems Material
handling is characteristically manual
Separate limitations for BOD5, COD, phenols, and TSS are developed
for each of the subcategories.
In establishing effluent limitation guidelines and new source
performance standards for the organic chemicals industry (113),
the EPA subcontractor reviewed and summarized historic treatment
plant data. Based on that information, conclusions were made
relative to the reduction of effluent constituents according to
three levels of treatment technology:
• Best Practicable Control Technology Currently
Available (BPCTCA)
0 Best Available Technology Economically Achievable
(BATEA)
• Best Available Demonstrated Control Technology
(BADCT)
A summary of the treatment plant survey data for exemplary
plants is shown in Table 15 (149). The average reduction in COD
was 72 percent; average reductions in BOD and TOC were 87 and 58
percent, respectively. To meet BATEA treatment guidelines, the
EPA has called for an effluent concentration of 10 mg/£ TSS, as
well as 69 and 90 percent reductions in BOD and COD, respectively.
For BADCT treatment, the EPA recommends the following level
of performance above the BPCTCA level:
Percent Reduction Minimum Monthly
Factors Beyond BPCTCA Average Effluent
Parameter Effluent Limitation Concentration
(mg/£)
BOD 17 10
COD 20
TSS 0 10
•
Additional parameters surveyed during the EPA guidelines study
included phenols, ammonia nitrogen, cyanide, sulfates, and pH.
Pulp and Paper Milling
Prior to the passage of the 1972 Amendments to the Federal
Water Pollution Control Act, to facilitate processing of the
Refuse Act discharge permit applications, the EPA had assembled
criteria for the pulp industry. These criteria (Effluent
limitation Guidance) were distributed on June 9, 1972. The EPA
48
-------
TABLE 15. TREATMENT PLANT SURVEY DATA* (113).
Plant 1
No.
2**
3**
**
4
5**
6**
**
8
g**
11**
. 13**
16**
17**
**
18
**
19
**
20
21
22
23
0
Average
COD
System
AS-AL
AS
AS
TF-AS
AL
AL
AS
AS-AL
AS
AS
AS
AS
AS
AS
AL
AS
AS
Category
C
D
B
B
B-C
B
C
C
B-C
D
D
D
D
C
C
B
B
% Removal
64
71
57
59
66
69
75
94
65
54.8
60.0
77.3
22.1
59.5
96.2
62
16.1
95.4
72
Effluent
mg/t
2,300
284
214
133
980
92
595
337
940
1,650
1,400
1,000
2,680
5,100
317
600
1,370
147
Total BOD
% Removal
90
73
82
92
73
84
92
99
90
82.1
81.4
90.0
16.7
69.8
99.5
78
47.5
92.6
87
Effluent
mg/£
427
74
13
12
235
6
75
16
177
300
240
310
650
1,800
19
27
210
41
TOC
% Removal
mg/t
32
71
35
43
11
26
69
27
64
80.8
63.4
76.8
55.8
96.6
66
8.3
95.4
58
Effluent
mg/t
2,710
132
80
61
573
52
242
343
470
280
410
360
1,025
1,700
114
47
550
35
TSS
% Removal
Negative
Negative
40
97
Negative
99
Negative
Negative
120
43.6
Negative
42.9
Negative
Negative
89
53.4
Negative
Effluent
mg/t
4,700
62
14
44
362
3
50
145
338
552
1,300
732
1,170
2,500
100
30
82
37
TDS
Effluent
mg/t
2,300
3,100
2,900
1 ,430
3,000
690
3,810
2,690
1,520
10,990
3,750
4,060
2,050
8,360
1,950
9,800
15,400
580
Oil & Grease
Effluent
mg/t
--
lf
4
2f
llf
--
12f
lf
6f
226T
24 1
22 1
1
106t
_-
.
19f
--
<.03:|:
21 |
* Based on 24-hr composite samples.
** Plants considered to be exemplary in performance based on historical data.
.toil arid grease are reported as carbon tetrachloride extractables.
rOil and grease are reported as Freon extractables.
* Includes exemplary plants as well as Plant 23.
-------
then authorized a study to provide additional information on
effluent limitations for the unbleached kraft, semi-chemical and
paperboard segments of the industry which was published as
proposed effluent limitations in the EPA Development Document in
January 1972 (102).
In 1976, the EPA published detailed guidelines for all major
subcategories of the pulp and paper industry (156). Subcategories
included groundwood, sulfite, bleached kraft, soda, deink and the
nonintegrated paper mills segment of the pulp, paper, and paper
board point source category. Effluent limitations for BPCTCA for
various subcategories as presented in the guidelines as shown in
Table 16.
Steel Making and Coal Gasification
The EPA has presented a development document outlining the
effluent limitations guidelines and new source performance standards
for the steel making segment of the iron and steel manufacturing
industry (38). Table 17 shows the derived maximum thirty-day
average effluent limitations for eleven subcategory processes
including by-product coke and beehive coke operations. Typical
products from the by-product type of operation include gas, tar,
tar acids, hydrogen sulfide, light oil, coke and coke breeze, In
the beehive process, only coke is produced and no other by-products
are recovered. Water is used only for coke quenching. The third
category which is numerically limited in oil and grease discharge
is the continuous casting processes which generate oily waste
products from machine cooling and spraying.
Textile Processing
Table 18 shows the maximum thirty-day average effluent
limitations guidelines for BPCTCA treatment for various process
categories of the textile processing industry (47). Commission
finishers are allocated 100 percent of the guidelines for the
thirty-day maximum levels. These types of operations process
material upon demand according to the customer's specification.
Control of production scheduling and process flows is therefore
difficult and subject to varying demand.
50
-------
TABLE 16. BPCTCA EFFLUENT LIMITATIONS IN kg/t (156)
Subcategory
Dissolving Kraft
Market Kraft
BCT Kraft
Fine Kraft
Papergrade Sulfite (Blow Pit Wash)
Bisulfite-Surface
Bisul fite-Barometric
Acid Sulfite Surface
Acid Sul fite-Barometric
Papergrade Sulfite (Drum Wash)
Bisulfite-Surface
Bisul fite-Barometric
Acid Sulfite-Surface
Acid Sul fite-Barometric
Continuous Digesters
Dissolving Sulfite
Nitration
Viscose
Cellophane
Acetate
Maximum
30-Day Average
BODs (mg/£) TSS (mg/£)
12.25 (24
8.05 (16
7.1 (14
5.5 (11
16.55 (33
.5) 20.05
.1) 16.4
.2) 12.9
.0) 11.9
.1) 23.65
18.05 (36.1) 28.1
16.8 (33
18.5 (37
13.9 (27
15.3 (30
15.5 31
16.9 33
19.85 39
21.55 (43
23.05 (46
25.0 (50
26.45 (52
.6) 23.65
.0) 28.1
.8) 23.65
.6) 28.1
.0 23.65
.8 28.1
.7 28.95
.1) 38.05
.1) 38.05
.0) 38.05
.9) 38.05
(40.1
Maximum
BOD5 (mg/£)
23.6 (47.2)
(32.8) 15.45 (30.9)
(25.8) 13.65 (27.3)
(23.8) 10.6
(47.3]
[21.2)
31.8 (63.6)
(56.2) 34.7
[69.4)
(47.3) 32.3 (64.6)
(56.2) 35.55 (71.1)
(47.3;
26.7
(56.2) 29.4
(47.3
56.2
(57.9
(76.1
(76.1
(76.1
(76.1
29.75
32.5
38.15
'53.4)
'58.8)
59.5)
65.0
76.3)
41.4 (82.8)
) 44.3 (88.6)
48.05
50.8 (1
[96.1 )
01.6)
Day
TSS
37.3
30.4
24.0
22.15
43.95
52.2
43.95
52.2
43.95
52.2
43.95
52.2
53.75
70.65
70.65
70.65
70.65
(mg/£)
(74.6)
(60.8)
(48.0)
(44.3)
(87.9)
(104.4)
(87.9)
(104.4)
(87.9)
(104.4)
(87.9
(104.4
(107.5
(141.3)
(141.3)
(141.3)
(141.3)
Qualified by
discharges.
allowances for barking, chip washing, log flumes or ponds, and noncontinuous
-------
TABLE 16 (continued)
Maximum 30-Day Average
Subcategory
GW- C hem i- Mechanical
GW-Thermo-Mechanical
GW-CMN Papers
GW-Fine Papers
Soda
Deink
NI Fine Papers
NI Tissue Papers
NI Tissue Papers (FWP)
BOD5 (
7.05
5.55
3.9
3.6
7.1
9.4
4.25
6.25
7.1
!mg/£)
(14.1)
(11.1)
(7.8)
(7.2)
(14.2)
(18.8)
(8.5)
(12.5)
(14.2)
TSS (mg/£)
10.65 (21.3)
8.35 (16.7)
6.85 (13.7)
6.3 (12.6)
13.2 (26.4)
12.95 (25.9)
5.9 (11.8)
5.0 (10.0)
9.2 (18.4)
BOD5
13.5
10.6
7.45
6.85
13.7
18.1
8.2
11.4
13.7
Maximum Day
(mg/£)
(27.0)
(21.2)
(14.9)
(13.7)
(27.4)
(36.2)
(16.4)
(22.8)
(27.4)
TSS (mg/£)
19.75 (39.5)
15.55 (31.1)
12.75 (25.5)
11.75 (23.5)
24.5 (49.0)
24.05 (48.1)
11.0 (22.0)
10.25 (20.5)
17.05 (34.1)
pH for all subcategories shall be within the range of 5.0 to 9.0
... **
Zinc
Subcategory
GW-Chemi -Mechanical
GW-Thermo-Mechanical
GW-CMN Papers
GW-Fine Papers
Maximum 30-Day Average
0.17
0.13
0.15
0.135
(0.34)
(0.26)
(0.30)
(0.27)
Maximum Day
0.34
0.26
0.30
0.275
(0.68)
(0.52)
(0.60)
(0.55)
**
Applicable only to mills using zinc hydrosulfite.
-------
en
OJ
TABLE 17. MAXIMUM THIRTY-DAY AVERAGE EFFLUENT LIMITATIONS
GUIDELINES: IRON AND STEEL INDUSTRY (38)
Subcategory
By-product coke
Beehive coke
Sintering
Blast furnace (Iron)
Blast furnace (ferromaganese)
Basic oxygen furnace (semi-wet
air pollution control methods)
Basic oxygen furnace (wet air
pollution control methods)
Open hearth furnace
Electric arc furnace (semi-wet
air pollution control methods)
Electric arc furnace (wet air
pollution control methods)
Vacuum degassing
continuous casting
Oil &
Cyanide Phenol Ammonia Sulfide Grease
Suspended
Solids pH
0.0219 0.0015 0.0912 — 0.0109
No discharge of process wastewater pollutants
0.0021
0.0078 0.0021 0.0651
0.1563 0.0208 0.5212
0.0365 6.0 to 9.0
to navigable waters.
0.0104 6.0 to 9.0
0.0260 6.0 to 9.0
0.1043 6.0 to 9.0
No discharge of process wastewater pollutants to navigable waters.
0.0104 6.0 to 9.0
0.0104 6.0 to 9.0
Mo discharge of process wastewater pollutants to navigable waters.
0.0104 6.0 to 9.0
0.0078
0.0052 6.0 to 9.0
0.0260 6.0 to 9.0
-------
TABLE 18. MAXIMUM THIRTY-DAY AVERAGE /
EFFLUENT LIMITATIONS GUIDELINES: TEXTILE MILLSV
FOR JULY 1, 1977 (47)*
Subcategory
(2 4)
Wool Scouring^ ' '
/A)
Wool Finishingv '
Dry Processing^ '
Woven Fabric Finishing
Knit Fabric Finishing^
Carpet Mills
Stock and Yarn Dyeing
and Finishing^)
^Reference 132.
^ 'Expressed as kg(lb)
t(1000
and Carpet Mills as
(A\
\^ >
4)
pol
Ib)
kg
BOD5
5.3
11.2
0.7
3.3
2.5
3.9
3.4
lutant except
product
(Ib) pollutant
t(1000 Ib) primary
(2)
v 'Oil and grease limi
TSS
16.1
17.6
0.7
8.9
10.9
5.5
8.7
Wool Scouring
backed carpet
tation for Hood Scouring is 3.6 k
COD
69.0
81.5
1.4
30-
30-
35.1-
45.1
42.3
as kg(
t'(
g(ib)
Total
Chromium
0.05
0.07
_ _
0.05
0.05
0.02
0.06
Ib) pollutant
1000 Ib) raw grease
Phenol
0.05
0.07
—
0.05
0.05
0.02
0.06
wool
Sul fid
0.10
0.14
—
0.10
0.10
0.04
0.12
JOOO Ib) raw grease wool
(3),
(4)
Fecal coliform limit for Dry Processing is 400 MPN per 100 ml.
For those plants identified as Commission Finishers, an additional allocation of 100 percent of the
guidelines is to be allowed for the 30-day maximum levels.
-------
PRACTICAL APPLICATIONS OF BIODEGRADATION OF ORGANIC INDUSTRIAL
WASTES
Several options are available for the treatment of organic
industrial waste streams. Physical and chemical pretreatment is
an important precursor to secondary treatment systems when there
are concentrated waste streams. At the Union Carbide Petrochemi-
cal Plant in Texas City, Texas, waste streams are segregated for
chemical recovery, incineration, stabilization, and other pre-
treatment processes. When the waste is so dilute that such pro-
cesses are no longer economical, it is sent to a secondary bio-
logical treatment plant.
An advantage to biological treatment is the degree to which
such systems can be adapted to the removal of residual dissolved
or colloidal organic contaminants. Where hazardous or toxic
organic constituents are present, biological transformations may
result in less innocuous compounds; the disposal of such process
residues will, therefore, be less restricted. Effluent limita-
tions guidelines research by the EPA (113) defines end-of-process
technology for new sources utilizing the best available demon-
strated control technology (BADCT) as biological treatment with
suspended solids removal via clarification sedimentation, sand,
or dual-media filtration.
Conventional Applications
Conventional applications of biological treatment to indus-
trial organic and hazardous wastes include most techniques used
for municipal waste treatment, e.g., activated sludge, aeration
basins, trickling filters, and stabilization ponds. Table 19
summarizes applications of conventional treatment schemes to
various organic industrial wastes, as described in the literature
Summaries of the efficiency and cost of biological waste treat-
ment schemes applied to petrochemical wastes have been prepared
(50). Applications of activated sludge, trickling filters,
aerated lagoons, and waste stabilization ponds to a variety of
organic chemical industries have also been described (47). Opera-
tional characteristics of activated sludge systems make them
highly amenable to concentrated waste treatment; their popularity
is well documented. Nevertheless, loading control and applica-
tion of predominantly biodegradable wastes to other treatment
schemes can also result in acceptable BOD and COD removal effi-
ciencies.
Innovative Applications
Innovative applications of biodegradation techniques for
treatment and disposal of organic industrial or hazardous wastes
are included in the following categories:
• Activated carbon adsoprtion with biological regeneration
• Biological seeding
55
-------
TABLE 19. APPLICATIONS OF CONVENTIONAL TREATMENT SCHEMES TO
VARIOUS ORGANIC INDUSTRIAL WASTES AS REPORTED IN THE LITERATURE
Description or Name
Activated sludge
(pilot)
Activated sludge
Activated sludge
(laboratory scale)
Activated sludge
Activated sludge
Activated sludge
plant
Activated sludge
plant
Activated sludge,
Aerated lagoon,
Trickling filter
Activated sludge,
Aerated basins,
Ditch aeration,
Rotating bio-
surfaces, Trickling
filters
Activated sludge
Trickling filters
Conventional
Waste(s) Applied
Ammonical liquor
from coke plant
Pump mill (USSR)
Ammonical liquor
and other waste
streams from
coke plant
Refinery pump &
paper pharmaceu-
tical
C^-Cg alcohols
Li ndane
Propylene glycol
wastewaters
PVC production
plant wastes
Categories B,
C, & D
Pulp, paper,
paperboard, mill
wastes
General petro-
chemical
M
Processes
Cost/Unit
Removal Efficiency Const.
92% TOC, 65% COD, p. 97-98
30% thiocyamate, jn ref.
55% cyanide
99.3% BOD5, 91.7% SS
99.1% phenols &
catechols, 99.4%
ammonium thiocyanate,
99.0% calcium thio-
cyanate
K values (see table)
75% BOD, 63% COD
90% TOD p. 132
(estimates
only)
in ref.
97% BOD in aer.
system
Source
Date
71
T973
142
1974
7
1967
4
1972
161
1974
168
1971
52
1971
113
1974
144
1976
50
1970
50
1970
Aerated lagoons
Stabilization ponds
56
-------
TABLE 19 (continued)
Conventional Processes
Description or Name Waste(s) Applied Removal Efficiency
Aerated stabiliza-
tion basin,
Non-aerated stabil-
ization basin,
Activated sludge,
Trickling filter,
Biofiltration,
Aerated lagoon,
Stabilization pond
Activated sludge
Anaerobic
Digestion
Trickling filter
Extended aeration
Air floatation to
aeration basin
Activated sludge
Aerated stabiliza-
tion basins, Ditch
aeration, Rotating
biological surfaces,
Trickling filters
Activated sludge,
Trickling filter,
Aerated lagoon,
Aerobic-facultative
penels
Pulp and paper,
industry effluents
Chlorophenolic
wastes
Parathion 2,4-D
wastewater (up
to 900 ppm)
malathion -BHC
chlorinated HC's
Herbicides
2,4-D, 2,4,5-T
(diluted 30 to 1
with municipal
-BHC
Synthetic rubber
laytex waste-
water
Pump and paper
milling process
effluents
BOD 87%
SS 84% for ASB and
AS
82% BOD
94% phenols
65% phenoxy-acids
95% lindane in
2 days
76% BOD, 62%
phenols
94% chloro-
phenols in 2
weeks
85% BOD, 85% SS
(p. 78)
Refinery, drinking
pharmaceutical,
kraft & sulfite,
paper, ammonia
still, black
liquor, paperboard
textile, chemical
Cost/Unit
Const.
p. 87
in ref.
Source
Date
102
T972"
74
1971
p. 85-88 82
in ref. 1973
p. 453-554 156
in ref. 1976
39
1966
57
-------
Fluidized-bed bioreactor
Fixed activated sludge
Deep tank extended aeration
Activated carbon addition
Pure oxygen systems
Deep shaft aeration
Limited aeration
Cooling tower bio-oxidation
Automation/optimi zation.
Each of these applications is included in one of the following
categories:
• Innovative bioreactor design (inherent innovation)
• Innovative accessories (external innovation) - often
applied to otherwise conventional treatment schemes
t Innovative operational methods.
A summary of applications, as reported in the literature, is
shown in Table 20. The reported removal efficiency for various
constituents, as well as retention time for each process and
average flow rate is presented in this table.
Innovative Bioreactor Design--
There are several desirable goals in altering or deriving
new designs for the waste treatment bioreactor unit. Two of
these are:
t Enhanced oxygen transfer to the microbiological cells
t Enhanced contact between wastes and microbiological cells.
There are, of course, benefits to be derived from accelerating
the biodegradation process: operational costs may be reduced;
less space may be required, resulting in decreased land costs;
and greater removal efficiencies can be effected.
Another goal to be considered in the design of innovative
biological treatment systems for concentrated industrial or hazard
ous wastes is the minimization of the toxic effects of certain
constituents upon the unit microbial population. Aeration basins,
for example, have been designed with long retention times and
complete-mix flow characteristics. However, recent surveys of
industrial waste treatment techniques (50) have shown that proper
pretreatment, the use of surge tanks or lagoons, and process con-
tori and housekeeping at source plants can have a significant
impact on treatment plant efficiency and stability.
58
-------
TABLE 20. APPLICATIONS OF INNOVATIVE TREATMENT SCHEMES TO VARIOUS ORGANIC WASTES AS REPORTED IN THE LITERATURE
Process
name
Activated
carbon :
anaerobic
regeneration
Activated
carbon :
aerobic
regeneration
Biological
seeding, pure
oxygen,
activated
sludge
Fluidized
bed bio-
reactor
(bench
appl ication)
Fixed
activated
sludge (pilot)
(also use of
biological
seed)
Waste(s)
appl ied
Textile
wastes
Textile
wastes
Herbicide
orange
Coal con-
version
effluent
(H2S,
Ammonia,
phenols ,
thiocy-
anate )
Munitions
manufactur-
ing wastes
(ethyl
alcohol ,
diethyl
ether,
DNT)
O&M costs/
unit con- Approx. Bioreactor
Removal stituent capital Avg. Retention
efficiency removed cost/yr flow time
49.4% BOD — -- 378,500 7-10 min
47.1-56.95! £/day (AC only)
COD
42.4-49.5%
TOC
(includes pre-
equalization)
75% COD 0.24/lb $550,000 3.79 x 1 O6
(theoreti- (1971)
-------
TABLE 20 (continued)
Process
name
Deep tank
extended
aeration
Activated
carbon
addition
Pure oxygen
activated
sludge
Pure oxygen
UNOX
Deep shaft
aeration
Deep shaft
aeration
Uaste(s)
appl ied
Refinery
storm
runoff
ballast
water
Petrochem
+10%
sanitary
Pulp and
paper
Textile
petrochem
Chemical
Pharma-
ceutical
Wood pulp
O&M costs/
unit con-
Removal stituent
efficiency removed
94% BOO 0.11 /kg
84% SS 0. 1 5/kg
Approx. 90% $0.26-
BOD 1.21/lb
89% BOD
84% SS
97% BOD
89% BOD
79% BOD
Approx. Bioreactor
capital Avg. Retention
cost/yr flow time
2,000,000/ 11-189 19 hr
1973 x 10°
I/day
3.79rx
105
£/day
150,000 35 min
IGPD
$2.5 mil/76 1.55 x 106 1 day
C/day
$2.5 mil/87 5.7 x 106 4.3 hr
£/day
$1.9 mil/76 8.7 x 106 2 hr
Approx.
Influent
mg/£
130 mg/£
1700 BOD
3200 COD
2500 MLVS
140
16900
3000
2300
Source
date Category*
135 A
1974
1 B
1974
156 A
1976
56
21 A
1976
19 A
T976
-------
TABLE 20 (continued!
cr>
Process
name
Series lagoons
anaerobic -
aerobic -
facultative
Anaerobic
stabilization
to aeration
basins
Anaerobic
stabilization
and aerobic-
anaerobic
ponds
Cooling towers
Wet composting
with bio-
logical growth
Waste(s)
applied
Petro-
chemical
dilute
Butadiene
ethyl ene
oxide
phenol
cumene
poly-
ethylene
bisphenol-
A
Chemical
paper
textile
Refinery-
dilute
Acetibem
phenol
p-cresol ,
di-Test-
butyl-
p-cresol
dicumyl-
peroxide
O&M costs/
unit con-
Removal stituent
efficiency removed
88-92% BOD .W/kg BOD
.044tf/kg BOD
.0354/kg BOD
80% BOD 0.064/kg BOD
89% BOD
50% BOD
44% BOD
80% BOD (survey)
98% phenol
92-97% BOD
100% volatile
acids
Approx. Bioreactor Approx.
capital Avg. Retention Influent Source
cost/vr flow time mg/£ date Category*
1.9 x 106 66-.'
-I n'j f\
$0.5 mil/81 t/day Approx. 800 BOD ly/^ A
20 days
o 7q y In7 (entire
$2. 2 mil/71 l/day system)
$4.7mi1/71 9.5^107
Approx. 1.6 x 107 15 days 1400 BOD ^L A
$3 mil. I/day ly/J
65 days — 39 A
18.4 days 1976
3.5 days
(survey) (survey) -- — 50
1970 B
-------
TABLE 20 (continued)
en
ro
Process
name
Waste(s)
appl ied
Removal
efficiency
O&M costs/
unit con-
stituent
removed
Approx.
capital
cost/yr
Avg.
flow
Bioreactor
Retention
time
Approx.
Influent
mg/i
Source
date Category*
Automation/ Glycol (Technology -- -- -- -- -- ^69
optimization wastes descriptions 1975
nutrient only)
addition
F/m control
floe control
biological
inhibitor
detector
(pilot)
* Category:
A = Innovative bioreactor design (inherent innovation) or additional biological stages
B = Innovative accessories
C = Innovative operational me1*ods
-------
Deep Shaft Aerati on — Systems designed around a plug flow
concept also utilize increased oxygen transfer with pressure to
eliminate short circuiting and to enhance biological degradation
(19, 21). Experimentation with U-tube aeration for sanitary sewer
systems indicated that this process has low land and operational
costs and can be installed without problems in relatively unstable
soil with a high groundwater level (110). A variation on the
U-tube process is known as deep shaft aeration (Figure 7). Such
systems, which include sufficient retention time for bioconver-
sion, are successfully treating textile, petrochemical, pharmaceu-
tical, and wood pulp process wastes in the United States, Canada,
the United Kingdom, and Germany. Typical operating conditions
and plant efficiencies for a deep-shaft aeration plant are shown
in Table 21.
Pure Oxygen Applications—Pure oxygen systems are innovative
bioreactor designs that can enhance oxygen transfer into the
aqueous phase. The most widely applied form of this technology
in both pilot and full-scale treatment plants is a pure oxygen-
activated sludge system. The use of high purity oxygen for
oxygenation of pulp, paper, and paperboard milling wastes has been
successful (156).
It is reported that closed activated-sludge plants can oper-
ate at very high active sludge levels (5,000 to 7,000 mg/£), and
dissolved oxygen concentrations (greater than 5/mg/£), and with
high overall utilization of oxygen feed gas (greater than 90 per-
cent), frequently reducing BODs levels to less than 30 mg/£. As
in the deep shaft process, the quantity of secondary sludge pro-
duced at the mill plants is reported to be less than is generated
by conventional activated sludge. Moreover, it can be success-
fully concentrated with minimal conditioning.
Figure 8 is a schematic diagram of a Union Carbide Corpora-
tion UNOX pure oxygen activated sludge system. Oxygen gas is fed
in during the first stage at a pressure slightly greater than
ambient. Recirculating gas blowers in each of the three unit
stages pump oxygen to a rotating sparger; pumping action of the
impellers located on the same sparger shafts maintain longer
residence time for the gas bubbles. Gas is usually recirculated
within a stage at a higher rate than the rate of gas flow from
one stage to another. The rate of gas transfer is controlled by
the oxygen demand in each. Each stage is covered to contain the
oxygen and off-gases (chiefly C0£ and N~).
Although the cost of energy for mechanical oxygen diffusion
is greatly reduced compared to conventional air systems, some of
these savings are negated by the energy required to produce the
pure oxygen supply. Nevertheless, within a range of process
scales, savings will outweigh the additional cost of oxygen pro-
duction hardware and operation. This range of cost-effectiveness
is further dictated by the quality and constituents of the waste
stream.
63
-------
cr>
RECYCLE SLUDGE
COMMINUTOR
RAW
SEWAGE
I
D
BAR SCREENING
AIR
COMPRESSOR
DOWNCOMER—'
I
DEEP
SHAFT
-RISER
Ill III
,K| "II I I II
L4 n
v| ' ' i1 1'i'i
^1 f? . . . ' ,
^ - i-^y FLOTATI
^r
RECEIVING
WATERS
FLOTATION
TANK
WASTE
SLUDGE
Figure 7. Example of a deep shaft aeration plant treatment scheme.
-------
TABLE 21. OPERATING CONDITIONS AND PLANT EFFICIENCIES
FOR A DEEP SHAFT AERATION PLANT
Raw sewage food (IGPD) 150,000
Shaft residence time (min.) 35
MLSS (mg/£) 6,000
Daily BOD load (kg/day) 484
F/M ratio (day"1) 1.4
Average
Concentration
Inlet
BOD5 140
Suspended Sol ids 190
Outlet
Whole BOD5 15
Filtered BOD5 5
SuspendedSolids 30
65
-------
en
en
CONTHOL
VALVE PRESSURE SIGNAL
GAS RECiriCULATION
COMPHESSOHS
OXYGCN
VTNT
RETURN ACTIVATED SLUDGE
WAS1E
ACTIVATED SLUDGE
Figure 8 . Schematic diagram or three-stage UNOX system.
-------
On-site oxygen production for pure oxygen-activated sludge
is not only feasible but is being practiced on a full-scale basis.
High pressure molecular sieve systems are used to separate oxy-
gen and nitrogen, producing a relatively pure oxygen source. For
larger scale plants, cryogenic air separation processes are often
applied: the liquefaction of the air is followed by fractional
distillation separating the air into oxygen and nitrogen compo-
nents (55). If there is a process ozonator-contactor-decomposer
at the plant, oxygen may also be derived from the destruction of
exhaust ozone. Wastewater treatment using conventional air-acti-
vated sludge has been compared with treatment using pure oxygen-
activated sludge at both pilot and full-scale plants (85). The
reported advantages of the pure oxygen method relate to sludge
quality, sludge production, required detention time for treat-
ment, and economies of scale. A comparison of process design
conditions for the two technologies is shown in Table 22.
It is also reported that the UNOX system has good process
stability when exposed to peak loading or shock loading, because
of the higher dissolved oxygen (DO) maintained in the bioreactor
unit (53).
Studies of the treatment of petrochemical wastewaters using
the UNOX process have been documented. Further comparisons
between the UNOX and conventional air-activated sludge systems are
shown in Table 23. The data are based upon a hypothetical petro-
chemical wastewater with an average flow of 6 MGD, a peak flow
of 6.25 MGD, and the following characteristics:
Parameter Average Peak
Sewage Temperature, °C 95 95
BOD5 Concentration, mg/l 1,000 1,240
kg/day (Ib/day) 110,000 (242,500) 142,153 (313,400)
COD Concentration, mg/t 2,500 3,100
kg/day (Ib/day) 275,000 (606,300) 355,384 (783,500)
SS Concentration, mg/£ 150 150
kg/day (Ib/day) 16,500 (36,380) 17,160 (37,830)
pH 7.0 7.0
A summary of treatment efficiencies for various petrochemicals and
wastes using the UNOX system is shown in Table 24.
Deep tank aeration--Deep tank extended aeration is practiced
at an Atlantic Richfield refinery in East Chicago, Indiana, which
produces aqueous wastes from a variety of refinery operations
(135). Combined refinery wastewater and surface runoff water
averaging 19,000 m3/day (5 MGD) is initially treated in API-type
67
-------
TABLE 22. COMPARISON OF PROCESS DESIGN CONDITIONS FOR
THE "UNOX" SYSTEM AND FOR CONVENTIONAL AIR AERATION
SYSTEMS FOR TYPICAL MUNICIPAL WASTEWATER
Mixed Liquor D.O. Level - mg/C
Aeration Detention Time (raw
flow only) - hr
MLSS Concentration - mg/C
MLVSS Concentration mg/C
Volumetric Organic Loading -
kg/1000 m3
Food/Biomass Ratio - kg BOD/
kg MLVSS
Recycle Sludge Ratio - kg
recycle/kg feed
Recycle Sludge Concentration -
mg/C
Sludge Volume Index
(M o h 1 m a n )
Sludge Production - kg VSS/kg
BOD removed
"UNOX"
Oxygenation
System
0.4-1.0
0.2-0.5
Conventional
Air Aeration
Systems
1-2
3-8
4,500-8,000 1,000-3,000
3,500-6,000 900-2,600
2,400-4,000 480-960
0.2-0.6
0.3-1.0
15,000-35,000 5,000-15,000
30-70
0.4-0.55
100-150
0.5-0.75
68
-------
TABLE 23. "UNOX" VS CONVENTIONAL AIR
ACTIVATED SLUDGE (56)
Conventional
UNOX System Air System
OPERATING POWER BMP
Oxygen dissolution 450 1,990
Oxygen generation* 678 --
1,128 1,990
INSTALLED POWER, NHP
Oxygen dissolution 510 2,250
Oxygen generation 900 --
1,410 2,250
ENERGY REQUIREMENTS
Total operating KW - 911 1,648
Total yearly KWH x 10 7,980 14,436
EFFICIENCY
Dissolution transfer
efficiency (Ibs 02 diss./
BHP-hr) 5.42 1.52
System transfer efficiency
(Ibs 0£ diss./BHP-hr) 2.16 1.52
Overall transfer efficiency
(KWH/lb 02 diss. ) 0.35 0.55
CAPITAL COST
Aeration tankage 803,550 1,848,110
Clarifiers 355,790 387,600
Installation, location,
overhead, etc. 532,290 996,250
Engineering 109,800 209,000
Contingency 270,000 516,000
Oxygen plant installation 310,000
Oxygen dissolution and
generation equipment 2,000,000 829 ,000 (only
diss. )
TOTAL SYSTEM COST $4,381,630 $4,785,960
Source: 50.
*
Monthly average generation power.
69
-------
TABLE 24. SUMMARY OF "UNOX" SYSTEM EXPERIENCE WITH CHEMICAL AND PETROCHEMICAL WASTES
—I
o
Location
Tenneco Chemicals, Houston, TX
Union Carbide Corp., Tait, LA
Hercules, Inc., Wilmington, NC
Exxon, Baton Rouge, LA
DuPont, Chambers Works, NJ
Ciba Geigy, Cranston, RI
Chemagro, Kansas City, KS
Shellberre, France
Bayer (Elberfeld) Germany
Ciba Geigy, Switzerland
Union Carbide, Montreal, Canada
Union Carbide, Sistersville, WV
Mitsubishi (Kasei) Japan
Mitsutuat (Osaka) Japan
Sumitono Niihaka, Japan
Fuji Film (Odawara) Japan
Kyowa Yuka Yokkaichi, Japan
Oasaka Gas, Japan
Union Carbide, Antwerp, Belgium
Shell, Rotterdam, Holland
Napthachimie, France
Lachema, CSSR »
Hoechat, Germany
Sandox, Switzerland
Shell, Norco, LA
Union Carbide, Brownsville, TX
Type Study
Pilot Plant
Pilot Plant
Pilot Plant
Pilot Plant
Pilot
Pilot
Pilot
Pilot
Pilot
Pilot
Pilot
Full
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Scale
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Treatability
Type of Waste
Acetylene
Various
Acetic & Formic Acids
Low weight acids &
alcohol
Various
Specialty Chemicals
Pesticides
Various
Various
Dyes
Petrochemical
Organosilicones
Ethylene Cracker
Various
Methionine W.W.
Alcohols
Acetaldehyde
Refinery
Ethylene oxide
production
Various
Petrochemical
Citric Acid
Petrochemical '
Pharmaceutical
Various
Acetic & Formic Acid
BOD
Applied BOD F/M
mg/£ day-MLVSS
Percent
BOD Removed
203
3,063
1,496
452
278
1,006
554
625
1,797
1,064
484
450
2,310
1,160
1,366
3,570
1,144
650
2,400
830
928
13,560
1,293
1,060
969
4,967
0.54
0.86
0.20
0.75
0.74
0.52
0.47
1.10
0.80
0.52
1.58
82
76
97
81
0.37
0.34
0.49
0.28
0.63
0.86
0.72
5-1.5
0.48
0.57
0.51
0.63
0.52
0.63
0.17
91
86
90
96
98
89
86
92
96 (soluble)
97 (soluble)
95 (soluble)
99 (soluble)
94 (soluble)
94 (soluble)
99
90
94
97
80
94
97
98
-------
oil/water separators before introduction into the deep tank sys-
tem. The deep tank aeration basins are followed by secondary
clarification. The process flow is split in half and delivered
to two bioreactors operating side by side, each 36.6 m (120 ft)
in diameter with a 7.3 m (24 ft) water depth. Aeration is accom-
plished by two aerators in each tank. Air is supplied to the
system by centrifugal blowers. There are three 250-hp (187 kw)
blowers, two normally in operation and one on standby. The design
air rate of the two bioreactors is 159 m3/min for each tank.
Complete mixing in such systems is usually maintained by air
diffusers, baffles, draft tubes, and other mechanisms. Operating
experience at this refinery indicated a removal efficiency of 94
and 84 percent for BOD and supended solids, respectively. The
yearly operating cost for processing 6.4 billion £/yr of refinery
wastewater was $80,820, resulting in a unit cost of $12.40/mi11 ion
t of wastewater processed. The utilities cost was approximately
$44,400/yr, maintenance $28,765/yr (high because of startup costs)
and operating labor $7,665/yr.
In this particular deep tank system, upset of the biomass by
toxins or corrosives never resulted in complete curtailment of
the operation. Experience also demonstrated that the system is
capable of achieving effluent criteria when hydraulically or
organically overloaded and is capable of treating variable waste
loads produced during normal refinery operations.
Laboratory studies of deep tank aeration (55) also indicate
that this type of innovative bioreactor design has potential.
Some of the areas in which potential capital savings can be
achieved with deeper tanks are:
• Less connected horsepower and blower capacity
• Fewer diffusers and less air distribution piping
• Less land and ancillary equipment such as distribution
and collection channels, return sludge systems, monitor-
ing, control and froth spray systems, walkways, and other
related structures. Probable savings in operating costs
include: less power, equipment and facility maintenance,
and lower interest and replacement costs. However, exces-
sive tank depths may interfere with adequate mixing.
Under such conditions, the air required for mixing may
exceed that required for transfer and dispersion forces
may inhibit floe formation.
Fluidized-bed bioreactors--Both the tapered fluidized-bed
reactor and the fixed activiated-sludge processes described below
utilize microorganisms adhering to some type of solid media in
the bioreactor chamber. Several examinations of the effects of
71
-------
solid surfaces upon microbial activity have been conducted (61,
172). Under experimental conditions, it has been shown that sur-
faces enable bacteria to develop in substrates otherwise too
dilute for growth. Development occurs in the form of epiphytic
slime or colonial growth. Enhanced COD and BOD removals have
been attributed to the presence of biologically active slimes.
In addition, some bacteria are actively sessile, attaching them-
selves to surfaces during the early logarithmic phase of growth
rather than during later growth phases. It has been suggested
that food particles are more available to cells on solid surfaces
where the interstices at the tangent of the bacterial cell and the
solid surface retard the diffusion of exoenzymes and hydrolyzates
away from the cell. Inert materials that support microbes in the
bioreactor in continuous fermentation processes also tend to pre-
vent the loss of microbes with removal of spent liquor, making
heavy loading of fresh substrates possible.
Tapering of the fluidized bed containing anthracite coal
would probably expand the range of optimum operation conditions
(141). Otherwise, it would be difficult to maintain nonfluctu-
ating operating conditions, since there are frequently high bed
expansion and low stability- However, in a tapered reactor, if
the cross section of the entry zone is sufficiently small and
expansion is gradual, the flow profile throughout the reactor
will be uniform and have fewer eddies.
A bench-scale fluidized reactor is operable under varying
conditions of air or oxygen addition (Table 25). Gas is applied
at the column bottom or to the feed waste stream. Under ideal
conditions and using a mutant strain of pseudomonas, the bench-
scale fluidized bed is very efficient in the removal of phenol.
Bench-scale experiments with the degradation of phenolic
waste by f1uidized-bed bioreactors has also been reported by
Holladay (64).
Anaerobic digestion-equa1ization--Several full-scale treat-
ment schemes utilizing anaerobic stages have been described in the
literature and are shown to be effective in petrochemical waste
processing.
The ecological relationships in anaerobic processes can be
complex. In lagoon systems, there is a large surface'area to
volume ratio; substantial amounts of oxygen can be introduced into
the near-surface waters by infusion or wind mixing. Many anaero-
bic primary treatment stages are operated as parallel fill and
draw basins, and some infiltration of liquid wastes into the soil
may occur. Natural bacterial activity, primarily anaerobic and
facultative, stabilizes the organic matter in the stored waste-
water through conversion and stabilization (Figure 9). The favor-
ing of anaerobic conditions minimizes production of cell mass.
72
-------
TABLE 25. PHENOL DEGRADATION RATES IN TAPERED
FLUIDIZED BED BIOREACTOR (141)*
Feed
Flow Rate
m£/min
409
425
412
475
480
482
500
505
374
388
391
C4. **
Stream
Phenol
Concentration
ppm
14
38
140
9
17
20
35
31
30
58
63
Effluent
Phenol
Concentration
ppm
0.05
<1
100
<0.025
.050
.050
<1
10
<0.025
<0.050
0.50
Reactor
Conversion
Ratet
g/day/£
2.4
6.6
6.9
1.6
3.0
3.9
6.6
6.6
4.6
9.3
10.2
Method of Oxygenation
Air sparge in column
Air sparge in column
Air sparge in column
Feed stream saturated
with 02 at ambient
pressure
Feed stream saturated
with 02 at ambient
pressure
Feed stream saturated
with 02 at ambient
pressure
Feed stream saturated
with 02 at ambient
pressure
Feed stream saturated
with 02 at ambient
pressure
Feed stream saturated
with 0? at 40 psig
Feed stream saturated
with 02 at 40 psig
Feed stream saturated
with 02 at 40 psig
All runs were made at ambient pressure, 25 ± 2°C, pH 7.0-7.2.
*In all tests, recycle effluent was used with a primary feed stream containing
450 to 4,800 ppm of phenol.
^Most sensitive assays of less than 1 ppm had a sensitivity of 0.025 ppm. The
less sensitive assay had a sensitivity of 1 ppm.
^Included the volume of the fluidized bed, as well as the volume of solution
above the bed and the volume of the settling chamber.
73
-------
COMPLEX
ORGANICS
ACID
FORMING
BACTERIA
£
ORGANIC
ACIDS
J V
METHANE
FORMING
BACTERIA
V
FIRST STAGE
(WASTE CDNVERSTION)
SECOND STAGE
(WASTE STABILIZATION)
Figure 9. Two stages of anaerobic waste stabilization (100).
-------
McCarty (100) indicates that the design parameters, and process
limitations of anaerobic treatment are dependent upon the micro-
bial and biochemical components. Intermediate acid formation is
dependent upon facultative and anaerobic bacteria. Litter reduc-
tion in BOD is achieved, but acids are formed, and some cell
material is generated. It is primarily the methane-forming bac-
teria that stabilize the oxidizable organ i c s. Sixteen grams of
methane evolved from the stabilization of a given waste correspond
to the removal of 64 g of ultimate BOD or COD. The variety of
symbiotic and competing biological and abiotic reactions that
characterize an anaerobic treatment lagoon is shown in Figure 10.
As indicated by Hovious et al. (65), anaerobic digestion-
stabilization is particularly effective in treating some petro-
chemical waste components such as low-molecular-weight acids and
alcohols. Such materials may enter the two-stage fermentation
process and be directly converted to methane. Destruction of the
acids by methanogenic and photosynthetic purple sulfur and non-
sulfur bacteria helps maintain an acceptable pH in the biological
treatment steps.
Another important phenomenon closely related to anaerobic
fermentation of waste materials is the sulfur cycle. A variety
of bacteria utilizes the sulfate materials in wastes as an elec-
tron donor during the oxidation of organic materials. Desulfovibrio
desulfuri cans performs such a reduction of sulfates. The H2$ pro-
duced by the reduction of sulfate or other sulfur-containing
materials is the cause of the "rotten egg" odor occasionally
associated with anaerobic treatment. However, biochemical and
abiotic chemical reactions occurring under anaerobic or aerobic
conditions work to control odors by utilizing the sulfide materials.
If oxygen is introduced to previously anaerobic zones, autoxida-
tion of sulfides may occur. Bacteria of the family thiobacteriacae
are chemosynthetic organisms that can oxidize sulfide compounds
or elemental sulfur to sulfate, but, with few exceptions, are
aerobic. Bacteria of the family thiorhodaceae, capable of pro-
ducing bacteriochlorophyl1, are anaerobic or microaerophi1ic-
Their photosynthetic metabolism utilizes reduced sulfur compounds
such as hydrogen sulfide to serve as the hydrogen donor during
the reduction of C02- This form of biooxidation of sulfides
usually results in the production of elemental sulfur droplets
inside the individual bacterial cells.
Work by Hovious et al. at two full-scale anaerobic lagoons
treating petrochemical wastes indicates that lagoon performance
is correlated with volumetric-organic loading and temperature (65).
Monitoring with gas-liquid chromatograph showed removal of speci-
fic organic materials (Table 26). Two lagoon loading rates were
evaluated, one with a concentrated waste (15,000 mg/£ COD) and
one with dilute waste (1,500 mg/i COD). The more lightly loaded
lagoon treating concentrated waste showed a lower effluent
75
-------
CTi
N,
140,
+T '
INFLUENT
INORGANIC CARBON
NITROGEN + PHOSPHORUS
VISIBLE
LIGHT
it
CO,
ATMOSPHERE
4
METHANE
ALGAL PHOTOSYNTHESIS
SOLUBLE ORGANICS
SETTLEABLE ORGANICS
CO,
CO,
AEROBIC DECOMPOSITION
SOLIDS
AC
DS
SOLUBLE ORGANICS
ANAEROBIC DECOMPOSITION
HUMUS
//\v/
EFFLUENT
ALGAE^
NITROGEN*
PHOSPHOR!) SL
SOLUBLE ORGANICS,
INORGANIC CARBON
BACTERIA
THERMOCLINE
OXYPAUSE
Figure 10. Possible biological and chemical reactions in
anaerobic treatment lagoon processes.
-------
TABLE 26. REMOVAL OF SPECIFIC ORGANICS IN ANAEROBIC LAGOONS*
Dilute Wastes,
208.6
kg/day/ 1 000 nr3
Influent Effluent
Compound
Methanol
Ethanol
n-Propanol
Isopropanol
n-Butanol
Isobutanol
n-Pentanol
Isopentanol
Hexanol
Acetaldehyde
n-Butyraldehyde
Isobutyraldehyde
Acetone
Methyl ethyl ketone
Benzene
Ethylene glycol
Acetic acid
Propionic acid
Butyric acid
(mg/i]
80
80
--
60
--
--
— ~
--
30
--
--
90
10
10
135
215
--
1 (mg/£)
35
15
--
30
--
—
™ ™
--
10
--
--
60
5
5
30
220
--
Influent
(mg/i)
380
270
170
175
170
250
315
140
80
190
210
150
--
—
755
2,120
0
0
Concentrated Wastes
353 kg COD/1000 m3
Effluent
(mg/£)
135
120
35
45
75
80
70
20
35
50
50
80
--
—
155
2,280
505
330
770 kg COD/1000 m3
Effluent
(mg/£)
145
130
40
55
80
85
100
30
40
35
50
70
--
__
190
2,620
470
300
*Data are averaged from 5 to 12 occurrences in grab or composite samples.
Note: lb/day/1000 cu ft x 16 = g/day/cu m.
-------
concentration of constituents detected in the raw waste than the
heavier loaded lagoon. In experiments with pilot and full-scale
lagoon treatment of industrial organic wastes, it was also found
that optimum performance was at temperatures between 20° and
43°C (60). Specific performance data for lagoons where volume
varied from 0.19 to 1,700 m3 are presented in Table 27. The
anerobic-aerated-facultative lagoon scheme is also reported to
have economic advantages over conventional, completely mixed,
activated sludge. The anerobic-aerated stabilization system will
produce an effluent comparable to the activated-sludge plant; a
significant reduction in unit removal cost is also typical. How-
ever, high land requirements and reduced efficiency at lower
temperatures are some of the negative aspects of the scheme.
Construction costs for plants with daily flows of 1.9 (0.5),
3.8 (10.0), and 9.5 (25.0) x 10^ m3/day (MGD) are shown in
Table 28. A waste strength of 800 mg/£ BOD was selected for the
base case estimate (66). The operational costs given in Table 29
are for the same lagoon systems. Capital and operational costs
for a Union Carbide lagoon-type treatment system in Puerto Rico
have also been derived (59).
Innovative Accessories--
Fixed activated sludge (FAS)--Kato and Sekikawa first des-
cribed the application of the fixed activated sludge (FAS) bio-
logical treatment process to industrial wastes (81). An applica-
tion of the treatment process to munitions-manufacturing waste
is described in Albert et al. (4).
The FAS process was first devised to overcome bulking prob-
lems caused chiefly by the growth of filamentous microorganisms
in wastes from an octanol plant and a soft drink manufacturing
plant. Screens are inserted in the conventional activated-sludge
bioreactor to provide a substrate for sessile filamentous species
and to prevent excessive suspended biological solids carry-over
into the secondary clarifiers. In applying the system to muni-
tions wastes, researchers observed that the waste stream (pri-
marily ethyl alcohol, diethyl ether, and DNT) promoted growths
of filamentous microorganisms in the receiving streams. The
decision to utilize the FAS approach was a result of these obser-
vations. In pilot investigations, substrate removal efficiency
in terms of TOC, BOD, and COD was 81, 76, and 76 percent, respec-
tively, when the TOC was in the neighborhood of 100 ftq/l. The
operating F/M ration was 0.60 and the calculated k. value or
removal rate was 0.90 hr'l. The effect of the screen area was
also evaluated; it was reported that the screen area was limiting
when the influent TOC concentration was greater than 100 mg/£.
It was concluded that if a fixed activated-sludge unit is to be
designed to treat the particular munitions waste, provisions for
increasing the screen area available for colonization will enable
the operation of the system at higher organic concentrations, and
78
-------
TABLE 27. DATA FROM UNION CARBIDE PILOT AND FULL-SCALE STUDIES
10
Lagoon Volume, m3
Texas City 9.84 x 104
Plant
Texas City 4.2 x 105
Plant
Seadrift 6.8 x 105
Plant
Texas City 0.189
Plant
Temper-
a -f-i i >«n
Q t-U I C %
°c
__
--
--
_ _
--
--
28
22
16
24
29
27
21
31
13
8
30
20
43
48
31
27
20
31
Waste Strength,
mg/l
BOD
4510
4440
5500
2990
2685
2280
536
527
598
547
641
_ _
--
--
--
--
--
--
--
--
--
--
--
--
COD
8450
8440
--
5900
5960
4450
._
—
--
—
--
1360
1420
1300
1310
1410
1270
1385
1295
1410
1240
1330
1380
1245
Volumetric Loadings,
kg/1000 m3
BOD
151.8
144.7
105.9
14.1
12.5
19.0
12.0
14.5
17.7
22.6
20.8
__
--
—
-_
--
-_
—
—
—
-_
-_
-_
--
COD
278.9
278.9
--
27.2
27.2
35.3
__
—
—
--
141.2
148.3
134.1
137.7
148.3
134.1
141.2
134.1
148.3
127.1
137.7
144.7
130.6
Areal Loading,
kg/A-day
BOD
302
290
209
60
55
80
60
73
85
108
104
..
--
—
—
--
—
—
—
—
—
—
—
--
COD
545
545
--
119
120
154
—
—
—
--
436
454
418
423
454
409
440
416
452
399
426
443
400
Removal %
BOD
33
39
58
66
63
65
75
75
69
76
83
__
—
—
—
—
—
__
__
__
__
_ _
__
—
COD
30
31
—
46
42
29
__
_ _
__
--
56
50
60
38
30
54
46
48
23
57
43
46
56
-------
TABLE 27 (continued)
oo
o
o
Lagoon Volume, m°
Texas City 5.50*
Plant
Temper-
ature
°C
23
30
27
23
28
28
28
26
19
15
10
17
13
19
22
13
19
22
23
28
29
Waste Strength,
mg/£
BOD
580
550
490
680
630
—
1053
1480
1080
1080
1080
925
1390
1540
1500
1620
1390
1050
810
1040
1230
COD
1200
1100
1230
1260
1260
1620
2150
1930
2000
2160
2160
2160
3080
3400
3240
3000
3000
2300
1740
3020
3080
Volumetric Loadings,
kg/ 1000 m3
BOD
60.0
56.5
15.9
70.6
67.1
__
225.9
190.6
113.0
113.0
113.0
95.3
144.7
158.9
208.3
113.0
95.3
80.2
113.0
144.7
128.4
COD
125.2
113.9
128.4
131.6
131.6
168.5
449.3
401.1
208.3
225.9
225.9
225.9
320.9
353.0
449.3
208.3
208.3
158.9
240.7
417.2
320.9
Areal Loading,
kg/A-day
BOD
222.7
213.6
188.6
261.4
254.5
—
831.8
713.6
418.2
418.2
418.2
356.8
534.1
594.5
772.7
415.9
356.8
297.5
415.9
534.1
445.0
COD
463.6
422.7
477.2
488.6
486.3
622.7
1663.6
1486.4
770.5
831.8
831.8
831.8
1188.6
1306.8
1663.6
772.7
772.7
595.4
890.9
1545.5
1188.6
Removal %
BOD
47
73
76
67
73
--
30
20
45
48
43
54
34
40
52
46
52
68
62
62
54
1 ^TT
COD
24
42
52
53
52
50
30
19
37
42
40
45
30
33
37
32
37
49
45
38
42
*Lagoon of an irregular, prismoid shape. Effective depth computed as volume/surface area.
-------
TABLE 28. CONSTRUCTION COST. SUMMARY
ANAEROBIC-AERATED STABILIZATION SYSTEM (66)
System Component
Neutralization
Structural
Mixing
Reagent Storage
pH Control
Clarification
Structural
Mechanical Equipment
Anaerobic Ponds
Earthwork
Concrete Liner
Aerobic Basin
Earthwork
Concrete Liner
Aeration Equipment
Electrical Support
Facultative Ponds
Earthwork
Concrete Liner
Piping
Instrumentation
Building and Lab Equipment
Site Preparation
Land at $l,000/acre
Subtotal
Construction Contingency
Construction Cost
Cost/1 b BOD Applied
Cost/1000 Gal.
Plant
1.9 x 104
$ 6,800
3,000
30,400
12,000
20,700
20,700
70,800
1,900
63,800
10,000
45,000
22,800
36,500
15,400
38,700
30,000
34,000
22,000
9,000
$506,000
51,500
$560,000
168
1,120
Size (106m3/day)
3.79 x 104
$ 22,000
9,300
30,400
12,000
123,600
59,000
326,500
39,300
209,500
32,800
448,000
85,500
135,500
59,100
167,400
56,000
51,000
49,100
100,000
$2,016,000
209,000
$2,225,000
33
222
9.46 x 104
$ 51,000
15,500
60,800
24,000
279,300
146,000
516,500
104,300
368,300
77,100
900,000
194,000
323,000
239,000
412,600
115,000
70,000
93,600
230,000
$4,220,000
430,000
$4,650,000
28
186
1971 dollars.
81
-------
TABLE 29. ESTIMATED OPERATING COST
ANAEROBIC-AERATION STABILIZATION SYSTEM (60)
Operating Labor & Supervision
Technical Supervision
Day-Shift Supervisor
Operators
Laboratory Analysis
Mechanic-Instrument Man
Reagents
NHs - 1 Ib N/20 Ib BOD
H3P04 - 1 Ib P/100 Ib BOD
H2S04 - 3000 Ib - 93% Acid/MM Gal
**
Power
Aeration Horsepower x 1.15
Maintenance
2.0 Percent of Construction Cost
Operating Supplies
Annual Operating Cost
Sludge Disposal^
Amortize Investment - 20 yrs at 6%
Total Annual Cost
Cost/1000 Gallons
Cost/1b BOD Removed
Cost/1b COD Removed
Plant Size, 106 m3/iay
1.9 x 104 5.79 x 104 9.46 x 104
$
5,800
6,200
36,400
5,200
5,200
500
200
7,800
$ 17,500
12,500
72,800
18,000
10,400
10,000
23,800
150,000
$ 17,500
12,500
72,800
20,000
15,600
25,000
59,500
375,000
11,400
10,000
300
157,000
44,000
2,000
372,000
80,000
4,100
$ 90,000 $518,000 $1,054,000
20,000 25,000 70,000
49,000 194,000 405,000
$159,000 $737,000 $1,529,000
0.87 0.21 0.17
0.14 0.034 0.028
0.081 0.020 0.016
**
r!971 dollars
Power at $0.01 per kw-hr
Annual operating plus investment costs.
82
-------
less dilution or less basin volume will be required. It was also
noted that secondary clarification for such systems should be
designed to minimize wall effects upon the filamentous sludges.
SVI values were high and could indicate problems in this regard.
Experimental result comparisons of FAS with conventional activated
sludge are shown in Table 30 (81) for an octanol plant waste.
FAS requires aeration, and the economic advantages or competitive-
ness with other methods are not well established. The primary
advantage is the control of sludge bulking.
Biological regeneration of activated carbon--The use of bio-
logicaTprocessesfor theregeneration of activated carbon employed
for chemical treatment of two Rhode Island textile plant waste
streams has been mentioned above. Like other biological treatment
schemes utilizing solid substrates for enhancement of biochemical
reactions, the granular carbon in activated-carbon columns has
been observed to enhance biodegradation.
Pilot and full-scale treatment systems described thus far
operate in alternating contamination and regeneration phases.
During the contamination phase, the textile processing wastes are
passed through upflow columns, and organic materials are adsorbed
onto the carbon matrix. At one of the Rhode Island sites, anaero-
bic regeneration was induced by maintaining the columns in periodic
quiescent modes. The other site practiced aerobic regeneration by
introducing a viable, acclimated, dispersed bacterial culture in
an upflow mode. Dissolved oxygen in the culture was maintained
at a level greater than 2 mg/£ by aerators. Figure 11 shows the
schematic diagram for such a system (134).
In full-scale plant operations with anaerobic regeneration,
25 percent soluble TOC was removed in the contamination cycle with
an average flow of 3.6 x 10? m3/day (95,100 gal/day). It has been
shown that with an average flow of 2.8 x 10? m3/day (74,000 gal/
day) and a full 1.83 m (6.0 ft) bed depth, the projected removal
could be 35 percent. On each contamination-regeneration cycle,
47 percent of MLVSS or 10.7 kg (23.6 Ib) of MLVSS/6-hr treatment
cycle was removed, thus reducing the sludge handling problems.
Removal of dissolved COD was related to soluble TOC removal and
was approximately 13.3 kg (29.3 1b)/treatment cycle. It was fur-
ther demonstrated that total COD, dissolved COD, and MLVSS can
be closely related; the data of one can be used to check against
the data of the others. Auxiliary treatment units included
removal of primary solids and initial roughing of the high BOD
waste loads and final polishing treatment of the column effluents
for removal of remaining organics and color. Anaerobic regenera-
tion was determined to be capable of restoring carbon adsorption
capacity to 20.5 to 33.2 kg total COD/day/100 kg carbon. Analyses
of heavy metals in the raw wastewater showed them to be below
1.0 mg/£.
83
-------
oo
-pa
TABLE 30. EXPERIMENTAL RESULTS ON THE OCTANOL PLANT
WASTE TREATMENT BY VARIOUS PROCESSES
Process
BOD COD
mq/t mq/t
Effluent_ .
BOD COD BOD COD
mq/t mq/t, percent percent
Removal
DT
hrs
340
440
10
87
97
Usual activated sludge
process (N & P added)
Usual activated sludge
process (N, P, Mg, Ca,
Fe added
FAS process
Two stage treatment
Primary,
FAS process
Secondary,
Activated sludge ( 384)( 504) 19 149 99
*Loading was calculated from 1st stage (FAS) effluent
340
430
430
1,260
1,260
440
544
544
1,420
1,420
8
16
26
19
384
87
99
115
149
504
98
96
94
99
70
80
80
82
79
90
65
90
12
8.0
13
9.5
24
10
14
Influent
ff
1
ill iili
i S
III ii''!
I
^ _>•
S Aeration ^^v^x^
Tank Intermediate
Settl ing Tank
^/
U
I
)
sual Act
Operational conditions
observed in aeration tank
Loading MLSS
m3 /Ha*j
kg/m
0.7
1.0
0.8
1.1
1.3
3.0
0.7*
Effluent
2,870
2,500
SVI
172
96
4,250
174
Sludge Process
-------
oo
en
i
i
AEROBIC
RESERVOIR
(BIOREACTOR)
AIR
WASTE
INPUT
HX3-
1
I
TANK
1
^
"T
U L
TANK
2
-i !
TANK
3
A
TANK
TREATED
EFFLUENT
ACTIVATED
CARBON
Figure I I. Aerobic activated carbon treatment/regeneration
schematic flow diagram.
-------
An anaerobic regeneration system (134) also functions on an
alternating contamination/regeneration treatment cycle. The sys-
tem operates on a batch sequence basis: for 10 hr, the columns
are operating on a contamination cycle, and the filtered waste
effluent is discharged; for 14 hr, the columns are back-flushed
(regeneration cycle) on a recirculation basis with an aerobic
biological culture. During the contamination cycle, liquid flow
occurs through each carbon column in series in a downflow mode.
During the regeneration cycle, the biological culture flows in a
parallel pattern through the columns in an upflow mode. The
average results of the operation in terms of COD, TOC, and color
are summarized as follows:
Parameter
COD - mg/£
TOC - mg/£
Color
Raw
Influent
550
220
Treatment Plant
Effluent
280
115
Percent
Reduction
49.0
47.8
99.5
From pilot operations, costs were derived for a proposed
1 MGD plant operating at 50 percent COD and 75 percent TOD removal
efficiency. Based upon a 1971 estimate, the following daily
power and chemical costs were presented (134):
Treatment
50% COD Removal
75% COD Removal
Operating Cost
$83/day
or
2.2<£/l ,000 I
$231/day
or
6.U/1.000 I
The construction cost of a 1-MGD plant is estimated to be
Treatment
50% COD Removal
75% COD Removal
C_£S_t
$230,000
$550,000
86
-------
When amortization is fugured into operating costs (capital
recovery 20 yr at 8 percent per annum), the costs becomes:
Treatment Operating Cost
50% COD Removal $147/day
or
3.8*/l,000 I
75% COD Removal $384/day
or
10.U/1 ,000 £
Biological seeding—Biological seeding is sometimes econom-
ic a 11 y~TelTsTbTe~To~r~~continuous application to large industrial
waste treatment systems. Select microbial cultures have also
proven useful in serving as start-up seed for full-scale or pilot
plants, where specialized wastes are being degraded (164). In
addition, bacterial cultures have been applied to batch treatment
processes where concentrated wastes have been isolated in spill
ponds or equilization tanks. One manufacturer of a freeze-dried,
biochemical complex indicates that specialized mutant bacteria
can be applied with various nutrients to wastes from pulp mills,
chemical plants, refineries, petrochemical complexes, and tex-
tile plants. A special culture has also been developed that can
remove cyanide toxins from coking and chemical plant wastewaters.
Data on one group of freeze-dried bacterial cultures, called
Phenobac, are presented below:
Oil Refinery Waste
Treatment System
Type: Biological Filter/Activated Sludge
Aeration Time: 12 hr
Sedimentation Time: 4 hr
Sludge Return: 25% of influent flow
Treatment Schedule
1) Neutralize influent pH with NH.OH
2) Adjust influent C/N ratio to 10:1 with diammonium phosphate
3) Add PHENOBAC
Effluent
Before After
Parameter Influent PHENOBAC PHENOBAC
Flow, m3/day 1,500.0 1,500.0 1,500.0
BOD5, mg/l 520.0 95.0 11.0
COD, mg/l 730.0 110.0 75.5
87
-------
Effluent
Parameter
Total Sol ids, mg/l
Suspended Solids, mg/l
Dissolved Solids, mg/£
Oil , mg/l
Phenol , mg/£
Dissolved Oxygen,mg/l
pH
Inf1uent
536,
235,
301
205,
86,
0,
0
0
0
3
4
2
5.7
Before
PHENOBAC
229.0
34.0
195.0
20.9
15.7
3.5
6.9
After
PHENOBAC
96.5
8.5
88.0
1.5
4.0
4.0
7.2
Organic Chemical Plant
Treatment System
Type: Activated Sludge
Aeration Time: 10 hr
Sedimentation Time: 4 hr
Sludge Return: 33% of influent flow
Treatment Schedule
1) Add diammonium phosphate to reduce influent C/N ratio to
10:1
2) Add PHENOBAC
Effluent
Before
Parameter Influent PHENOBAC
Flow, MGD 1.5 1.5
BOD5, mg/l 1,200.0 335.0
COD, mg/l 1,815.0 360.0
Total Solids, mg/l 1,210.0 522.0
Suspended Solids, mg/l 260.Q 50.0
Dissolved Solids, mg/l 950.0 472.0
Cyanide, mg/l 18.0 10.0
Acrylonitrile, mg/l 52.0 18.5
2-Ethylhexanol, mg/l 225.0 100.0
Dissolved Oxygen, mg/l 0.2 0.7
PH 7.5 7.3
Kraft Mill Waste
Treatment System
Type: Oxidation Lagoons
Installed HP: 1,800
Aeration Time: 24 hr
Sedimentation Time: 8 days
After
PHENOBAC
1.5
16.0
215.0
188.0
13.0
0.0
0.0
0.0
0.8
4.4
7.0
88
-------
Treatment Schedule
1) Reduce influent pH to 7.5 with waste
2) Preaerate lagoon entrance channel with 150 HP aerator
3) Add 3 Ibs N/100 Ibs BOD to reduce influent C/N ratio to
10:1
4) Add PHENOBAC/POLYBAC
Effluent
Parameter
Flow, MGD
BODs, mg/£
Total Solids, mg/l
Suspended Solids, mg/£
Dissolved Solids, mg/£
Total Alkalinity, mg/£
Color
Dissolved Oxygen, mg/£
pH
Inf1uent
30.0
300.0
1,945.0
355.0
1,590.0
322.0
448.0
0.5
9.0
Before
PHENOBAC
30.0
84.0
425.0
135.0
290.0
125.0
420.0
0.1
7.5
After
PHENOBAC
30.0
42.0
358.0
12.0
346.0
19.0
17.0
3.5
7.3
Steel Mill Coking Hastes
Treatment System
Type: Trickling Filter/Oxidation Lagoons
Aeration Time: 10 hr
Sedimentation Time: 4 hr
Treatment Schedule
1) Adjust influent
2) Add PHENOBAC
pH to 7.1-7.2 with H3P04
Parameter
Flow, MGD
BOD5
COD,
Total Solids
Suspended Solids, mg/£
Dissolved Solids, mg/£
Phenol , mg/£
Cyanide, mg/£
NH3-N, mg/l
PH
Inf1uent
2.0
685.0
,175.0
680.0
235.0
445.0
880.0
25.0
:,000.0
10. 1
Effluent
Before
PHENOBAC
2.0
400.0
825.0
295.0
100.0
195. 0
46. 2
4.4
178.0
9.2
After
PHENOBAC
2.0
20.0
138.0
120.0
13.0
107.0
0.1
0.0
1 .3
7.1
89
-------
Textile Plants
Treatment System
Type: Activated Sludge
Aeration Time: 10 hr
Sedimentation Time: 4 hr
Sludge Return: 33% of influent flow
Treatment Schedule
1) Add diammonium phosphate to yield influent C/N ratio of
10:1
2) Add PHENOBAC
Effluent
Before After
Parameter Influent PHENOBAC PHENOBAC
Flow, MGD 2.0 2.0 2.0
BOD5, mg/£ 870.0 314.0 12.0
COD, mg/£. 976.0 422.0 325.0
Total Solids,mg/£ 1,400.0 835.0 442.0
Suspended Solids, mg/l 850.0 122.0 15.0
Dissolved Solids, mg/£ 550.0 713.0 427.0
Oil, mg/£ 36.0 21.0 0.5
Mixed Aliphatic Acids, mg/l 112.0 95.3 2.6
Dissolved Oxygen, mg/£ o.O 2.0 3.8
pH 7.1 6.1 7.2
Phenol Waste
Treatment System
Type: Activated Sludge
Aeration Time: 10 hr
Sedimentation Time: 4 hr
Sludge Return: 25% of influent flow
Treatment Schedule
1) Neutralize influent with NH4OH to pH 7.0-7.2
2) Adjust influent C/N ratio to 10:1 with diammonium phosphate
3) Add PHENOBAC
*
Effluent
Before After
Parameter Influent PHENOBAC PHENOBAC
Flow, m /day 1,500.0 1,500.0 1,500.0
BOD5, mg/£ 850.0 320.0 9.7
COD, mg/l 1,224.0 432.5 25.8
Total Solids, mg/l 1,200.0 535.0 336.5
90
-------
Parameter
Suspended Solids, m g / £
Dissolved Sol ids, mg/£
Phenol, mg/i
NH3-N, mg/£
Dissolved Oxygen, mgfi
pH
Influent
145.
095.
332.
0.
0,
5.4
Effluent
Before After
PHENOBAC PHENOBAC
55.0
480.0
107.0
9.6
2.5
7.1
22.0
314.0
0.02
1.1
3.8
7.0
Laboratory experiments indicate that these bacteria cultures
are also effective in degrading halophenols, aliphatic and aryl
amines and aryl halides. The manufacturers indicate that
Phenobac effectiveness will be greatly diminished unless the
wastewater treatment system meets the following conditions:
Parameter
Influent pH
Dissolved oxygen, mg/£
C/N/P
Temperature, °C
Toxic metals, mg/l
(e.g., hex. chromi urn)
Optimum Minimum
7.0
3.0+
100/10/1
30
4.5
2.0
None
10
None
Maximum
9.5
None
200/10/1
40
<2
Such limitations restrict the types of waste streams that
may be subject to innovative biological seeding. Furthermore,
continuous seeding must be conducted to maintain a viable degrad-
ing population where there are adverse environmental conditions,
other microbial predators, or excessive washout. The cost of
continuous additions of large volumes under such circumstances
may be noncompetitive with alternative treatment methods.
Powdered activated carbon treatment (PACT)--The results of
several full-scale tests of powdered activated-carbon addition
to a variety of chemical plant effluents is described by
A. D. Adams (1). According to Adams, the addition of powdered
carbon to waste streams prior to their introduction into aerated
or activated-sludge systems:
t Improves BOD and COD removals despite hydraulic and
organic overload ings
• Aids solids settling, decreases effluent solids, and
yields thicker sludge
t Adsorbs dyes and toxic components that are either not
treated biologically or are poisonous to the biological
system
91
-------
• Reduces aerator and effluent foam by adsorption of deter-
gents
• Prevents sludge bulking over broader F/M ranges
• Effectively increases plant capacity at little or no
additional capital investment
• Gives more uniform plant operation and effluent quality,
especially during periods of widely varying organic or
hydraulic 1 oads.
Test results with activated carbon at an ICI American facil-
ity manufacturing polyols and derivatives are cited. By adding
sufficient powdered activated carbon to maintain a level of
1,000 ppm in the 568-m3/day (150,050 gal/day) system, COD and
BOD removals were increased 25 and 20 percent, respectively.
In another test at a municipal waste treatment plant treating
70-percent industrial flow from a textile plant, activated car-
bon in the waste at 900 ppm effectively stabilized the variabil-
ity of BOD removals.
Adams further notes that there are presently no full-scale
wastewater treatment plants that regenerate spent powdered car-
bon on a continuous basis, although several have been suggested.
Experience showed that typical treatment costs for activated-
carbon addition can vary from 0.4 to 1.8 cents/1,000 I. Savings
may also be incurred since fewer defoamers, coagulants, and
coagulant aids are needed. Sludge conditions may also be
improved by the presence of the carbon.
Pilot testing of the DuPont PACT process at DuPont Chambers
Works organic chemicals plant is reported by Flynn (45). Research
indicated that removals of COD and TOC due to carbon alone can
be computed; such removals are likely to increase with sludge
age. Results of experiments with five continuous-flow labora-
tory PACT units treating a variety of high, medium, and low
sludge ages and temperatures are shown in Table 31. Additional
laboratory studies (80) have indicated that the activated carbon
effectiveness in activated sludge systems is primarily due to
surface concentrating effects in systems of dilute waste concen-
trations. The carbon can also adsorb toxins, thereby.reducing
the toxin concentration to a level where it is not inhibiting
and may be slowly degraded.
Cooling tower biooxidation--Coolinq towers can also supple-
ment conventional biological conversion. The enhanced surface
area of the tower and resultant increase in dissolved oxygen in
the cascading waste stream promote biological growth within
cooling towers. One cooling tower system reported in the litera-
ture (50) removes 1,727 kg (3,808 Ib) of BOD/day and reduces
92
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TABLE 31. CARBON ADDITION TO ACTIVATED SLUDGE - DUPONT PACT PROCESS (45)
(jO
Temperature (°C)
Residence Time
(days)
Sludge Age (days)
Feed Carbon
Concentrate (mg/£)
Feed BOD (mg/t)
Effluent BOD (mg/t)
Mixed Liquor
Suspended Solids
Biological TSS
(rngX-t)
Loading (mg BOD/mg
31
0.203
14.1
158.4
151
2.7
14,297
3,311
0.220
31
0.184
5.5
148.3
151
6.8
6,518
2,082
0.375
Summary of
25
0.254
13.4
152.1
153
2.6
10,667
2,630
0.224
Results
21
0.157
8.4
149.8
147
2.8
11,223
3,190
0.287
20
0.169
8.7
159
145
2.7
11,145
2,977
0.282
13
0.188
14.7
147.8
153
4.5
15,242
3,657
0.216
7
0.191
11.2
152
148
8.8
11,975
3,004
0.244
7
0.206
3.9
166
154
34.5
4,380
1,221
0.477
-------
the phenol concentration from 12 to 0.09 mg/£. A similar system
was reported to reduce the phenolic concentration from 3 to
0.06 mg/£. It was also noted that periodic blowdowns and system
cleaning due to biological sloughing result in high BOD slugs.
Biooxidation of reuse waters in a petroleum refinery has
resulted in considerable water quality improvement and subse-
quent reduction in water demand (112). However, care should be
taken to determine those organic compounds that are converted in
biological processes and those that are stripped into the atmos-
phere by the forced or induced air draft. This is especially
true for the volatile, less soluble compounds and may result in
secondary air pollution problems. The rate of corrosion of cool-
ing tower structures is not accelerated greatly because of the
accumulation of biological slimes and biooxidation processes.
Innovative Operational Methods--
Automation/optimization--Understanding of the mechanisms
and kinetics of biological waste treatment processes is continu-
ally increasing. As the interrelationships of various treatment
components are understood, treatment plant designers and opera-
tors are attempting to improve processes. Automation and feed-
back process control are being utilized more and more. Key
waste and operational parameters are being identified and charac-
terized. Many of these parameters may be continuously measured
or determined from automatic composite sampling. Signals from
continuous monitors or data from samples may be automatically
used to compute independent control variables or used to directly
control operational processes. Such systems are known as opti-
mal feedback control systems and rely heavily upon continuous
or semicontinuous sampling and automated process control. The
objectives of control actions are to maintain the desired rate
of byconversion in the bioreactor although other parameters,
such as suspended solids in the final effluents or cost of
chemical additions, may also be considered.
In waste treatment plants where computerized process opti-
mization is practiced, it is imperative that a process model
be defined in the control program. An understanding of the
kinetics of biological and chemical reactions is especially
important. A discussion of the development of modern optimal
feedback control models and their required inputs is presented
by Fan et al. (43).
Where real-world process monitoring inputs are not utilized,
process models may still be used in computer simulation studies
to determine optimum operational modes. Alternative models may
also be compared for selecting better operational methods (32).
94
-------
The application of treatment optimization through automation
at a Dow Chemical Company petrochemical plant was tested by Zeitoun
et al. (169). A summary of the system is presented below:
Instrumentation and control of an industrial,
activated-sludge pilot plant was accomplished by
development of systems controlling the critical
parameters of the process to achieve reliable, high
quality effluent. Optimization techniques based on
the steady-state and transient models of the acti-
vated sludge process were used to determine the
minimum volume of the aeration basin required for a
specified effluent quality and to predict the tran-
sient conditions as a result of step changes in
loading.
A pH control system stopped plant operations
for the duration of the upset, automatically restor-
ing it when the feed pH returned within operating
limits. An automated sampling system, sampling feed
and homogenized mixed liquor, monitored the total
carbon in both samples. Nutrients (nitrogen and
phosphorus) were added in proportion to the total
carbon in the feed, thus maintaining low residual
nutrients in the effluent. The sludge recycle flow
rate was controlled by a food to microorganisms (F/M)
signal, measured as the ratio of total carbon in the
feed to that in the mixed liquor. Response time of
the F/M control system to a step increase in feed
concentration was reduced by 50 to 70 percent, as
compared to the uncontrolled system, depending on
the amount of excess sludge available for recycle.
Chemical flocculants were added in proportion to the
turbidity of the biosettler overflow, removing 85 to
98 percent of the suspended solids. Toxic or inhibi-
tory effects of the feed were measured by a biological
inhibitor detector, an instrument that measures the
oxygen uptake of standard solutions before and after
exposure of a bacteria sample to a feed sample and cal-
culates an activity ratio, that had an automated cycle
of 60 min. The use of the instrument as an upstream
sensing device was demonstrated as toxic substances
were added to the feed (169).
Cost evaluations for such systems can vary greatly depending
upon the degree of automation and sophistication of the monitoring
and data analyzing hardware. In addition, most full-scale auto-
mation has been conducted only at a pilot level and it would be
difficult to make cost estimates for a full-scale plant. How-
ever, this technology will be used more and more in the future
to meet stringent discharge standards and avoid fluctuations in
95
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discharge loadings. Plant owners and operators will be better
able to evaluate the benefits that such systems may provide for
their particular plants.
MICROBIAL ASSIMILATION OF ORGANIC WASTES
There is relatively little information in the literature
describing microorganisms capable of metabolizing recalcitrant
organic materials. Most studies have considered mono-cultures
and idealized carbonaceous substrates applied under carefully con-
trolled laboratory conditions. Such experiments are not affected
by the same complex biochemical, ecological, and successional
relationships typical of anaerobic lagoons, sludges, aeration
basins, and other treatment plant environments. Moreover, analy-
ses of industrial treatment plant waste streams for microbial
populations do little to predict the efficiency of biodegradation.
Gross observations of these populations can be helpful in deter-
mining which orders of bacteria, actinomycetes, fungi, yeast, or
protozoa will predominate with known plant environments and waste
characteristics. Such information provides a foundation for
future studies of complex population interactions and has proved
useful in selecting proper microbial seeds for either starting or
accelerating biological treatment of certain organic wastes.
The results of a literature survey of microorganisms that
can assimi1 ate recalcitrant organic materials are shown in Table 32.
Appendix A presents a bibliography of material related to the
microbial assimilation of organic wastes. Extensive growth tests
conducted with various bacteria, fungi, yeast, and other microbes
on saturated hydrocarbons, aliphatics, aromatics, and hydrocar-
bon mixtures show Pseudomonas to be the most capable. Early
studies of microorganisms that can assimilate paraffin wax are
reported by ZoBel1 (170). His work shows that soils, sediments,
and water are the major reservoirs of hydrocarbon-degrading popu-
lations. The ability to metabolize hydrocarbon substrates appears
to be widespread; more than 200 species (28 bacterial, 30 filamen-
tous fungal, and 12 yeast genera) have been shown to utilize
hydrocarbons (31).
Organic chemicals and synthetics have also been demonstrated
to be amenable to biological degradation. Bayley and Wigmore
(13) have studied the growth of mutant strains of Pse\idomonas
Putida on phenol and cresols, and fungi have been observed grow-
ing in jet fuels (128) and toluene (115). Phenylmercuric acetate
has been shown to support growth of Pseudomonas, Arthrobacter,
Citrobacter, Vibrio, Flavobacteriurn, and Enterobacter. ZoBell
(171) reported the growth of actinomyces and bacteria on various
rubber compounds including polymerized olefinic hydrocarbons, raw
or crepe rubber, and hevea latex. Detergent compounds, particu-
larly linear alkyl benzyl sulfonates, are readily degraded in
waste treatment plants. Two bacteria genuses are responsible for
this decomposition: Nocardia and Pseudomonas (108).
96
-------
TABLE 32. LIST OF MICROORGANISMS REPORTED BY VARIOUS AUTHORS
TO ASSIMILATE RECALCITRANT ORGANIC MATERIALS
Reference
(See Appendix A)
Elevens and
Perry (1972)
Bayley and Wigmore
(1973)
Markovetz and
Kallio (1964)
Miller et al. (1964)
Scheda and Bos (1966)
Otsuka et al. (1966)
Lowery et al. (1968)
lida and lizuka (1970)
Barua et al. (1970)
Prince (1961)
Kester (1961)
Krause and Lange (1965)
Nyns et al. (1968)
Waste
Description
methyl amine
propane
phenol
cresols
hydrocarbons of
chain length C10-C,g
Microorganisms
Pseudomonas sp.
gram-negative diplococcus
Mycobacterium vaccae (JOBS)
album strains 7E4 and 7E1B1W
M. rhodochrous strains OFS, A78
and 7E1C
Mutant strains of Pseudomonas
putida (strain U)
Rhodotorula, Trichosporn,
Candida lipolytica and Candida
pulcherrima
chain length C,,,-C,0 Candida intermedia
I c I o
n-hexadecane
n-decane
kerosene
kerosene
hydrocarbons of chain
length C1Q-C16
n-alkanes
1-decene
paraffins
jet fuels
n-tridecane
n-alkanes C,,, C,n,
r r r c
L22' L23' 28' L32
hydrocarbons, toluene
Rhodotorula sp., Pichia,
Debaryomyces, Candida,
Torulopsis
Candida tropical is
C. tropical is, C. cloacae
Candida, Rodotorula, Debaryomyees
Candida rugosa
Trichosporon pullulans
Cladosporium, Hormodendrum
Aspergillus aliaceus, Cephalos-
porium roseum, Colletotrichum
altramentarium, Acremonium
patronii, Fusarium balbigenum,
and Monila bonordenii
three species of Fusarium
Fusarium, Penicillium, Paecilo-
myces, Chloridium, Oidiodendron,
and Scolecobasidium
97
-------
TABLE 32 (continued)
Author
Lowery et al. (1968)
Stone et al. (1942)
Webley (1954)
Treccani et al. (1955)
Walker and Colwell
(1974)
Nelson et al. (1973)
Makula and Finnerty
(1972)
Atlas and Bartha (1972)
Walker and Colwell
(1974)
Zajic and Knettig
(1972)
Scott and Hancher
(unpublished)
LaRock and Severance
Zobell (1969)
Waste
Description
hydrocarbons
various oils
n-dodecane,
n-tetradecane
n-hexadecane
n-octadecane
numerous compounds
from C,- C,.
Microorganisms
C3~C12
petroleum
"28
phenylmercuric ace-
tate
tetradecane
pentadecane
hexadecane
crude oil
petroleum
kerosene
phenol
hydrocarbon
mixture
kerosene
jet fuel
paraffin wax
Novelli and Zobell (1944) aliphatic hydro-
carbons
Aspergillus, Cephalosporium,
Dematium, Epicoccum, Fusarium,
Gliocladium, Graphium, Mucor,
Paecilomyces, Penicillum, and
Trichoderma
pseudomonads
Norcadia opaca
norcardia, mycobacterium
achromobacter
mercury-resistant strains of
Pseudomonas, Arthrobacter,
Flavobacterium Vibrio,
Citrobacter.
Pseudomonas, Arthrobacter,
Citrobacter, Vibrio, Flavo-
bacterium, Enterobacter
Micrococcus cerificans
Brevibacterium sp., Flavo-
bacterium sp.
Cladosporium resinae
Corynebacteri urn hydrocarboclastus
Pseudomonas Putida
Brevibacterium
Aspergillus, Botrytis, Candida,
Cladosproium, Debaromyces, Endomyces,
Fusarium, Hansenula, Monilia,
Penicillium, Actinomyces, Micro-
monospora, Nocardia, Proactino-
myces, and Streptomyces
Desulfovibrio
98
-------
TABLE 32 (continued)
Author
Waste
Description
Microorganisms
Mul kins-Phi Hips and
Stewart (1974)
ZoBell (1950)
Kaufman and Plimmer
(1972)
Mitchell
Mitchell (1974)
Cooper (1963)
Taber (1976)
Callely et al.
(1976)
Cooney and Walker (1973)
Ahearn
Gibson and Yeh (1973)
Ahearn
crude oils
caoutchouc
(polymerized olefinic
hydrocarbons)
Norcardia, Pseudomonas, Flavo-
bacter, Vibrio, and Acnromobacter
Actinomyces alba, A. chromogenes,
A. elastica, A. fuscus, Bacillus
mesentericus, Mycobacterium lac-
ticola, M. rubrum, and Pseudo-
monas fluorescens
raw or crepe rubber Serratia marcescens
plantation rubber/
hevea latex
aliphatic acids
w-phenoxyalkanoates
malathion
pesticides
detergents
rendering plant
wastes (anaerobic)
petroleum refinery
waste (anaerobic)
pulp mill wastes
industrial effluents
hydrocarbons
benzene
toluene
ethyl benzene
p-Fluorotoluene
p-Chlorotoluene
p-Bromotoluene
Naphthalene
biphenyl
Aspergillus and Penicillium
Alcaligenes denieri, Bacillus
pandora, Gaffkya verneti, Micro-
coccus chersonesia, M. eatoni,
M. epimetheus, M. ridleyi, and
Forulae heaveae
Norcardia sp.
Norcardia coeliaca
Tric'hoderma viride
Pseudomonas, Bacillus, Flavobac-
terium, and Achromobacter/Nor-
cardia, Aspergillus
Nocardia, Pseudomonas
Thiopedia rosea
Chromatium sp.
Azotobacter, Klebsiella, Rhodoto-
rula, Hansenula, and Pichia
Achromobacter, Alcaligenes, Como-
monas, Flavobacterium, Pseudomonas,
Thiobacillus and Zoogloea
Cladosporium resinae
Pseudomonas putida
Pseudomonas sp.
Beijerinckia sp.
99
-------
TABLE 32 (continued)
Author
Perry and
Cerniglia (1973)
Ahearn
Finnerty et al. (1973)
Ahearn
Soli (1'973)
Ahearn
Guire (1973)
Ahearn
Hollackov et al.
(1976)
Shelton and Hunter (1975)
Sivela and Tuovinen
Waste
Description
Microorganisms
petroleum
hexadecane
hydrocarbons
hexadecane
weak ammoniacal
liquors (coal coking)
oils (in anaerobic
sediments)
methyl mercaptan
dimethyl sulfide
dimethyl disulfide
Cunninghamella elegans
PeniciIlium zonatum
Aspergillus versicolor
Cephalosporium acremonium
Penicillium ochro-chlorens
Acinetobacter sp.
Arthrobacter sp., Mycobacterium
paraffinicum
Candida petrophilum
Pseudomonas aeruginosa
Bacillus, Stapholoccus (not aureus),
Pseudomonas, Citrobacter, Proteus
and E. Coli
Oesulfovibrio
thiobacilli
TOO
-------
TABLE 33. MICROORGANISMS KNOWN TO METABOLIZE ORGAMOCHLORINE PESTICIDES (152)
Reference
(See Appendix A)
Pesticides
Microorganism
Patil et al. (1970)
Patil et al. (1970)
McRae et al. (1969)
Mendel and Walton, (1966)
Fbcht, (1972)
Wedemeyer, (1966)
Patil et al. (1970)
Barker et al . (1965)
Patil et al. (1970)
Bourquin et al. (1971)
Matsumura et al. (1968)
Patil et al. (1972)
Lichtenstein and Schulz, (1959)
Chacko et al. (1966)
Chacko et al. (1966)
Chacko et al. (1966)
Focht, (1972)
Anderson et al. (1970)
Bixby et al . (1971)
Kallerman and Andrews, (1968)
Sweeney, (1968)
Patil et al. (1972)
Endrin, DDT
Endrin, DDT
Lindane
DDT
DDT
DDT
Endrin, Aldrin, DDT
DDT
Endrin, Aldrin, DDT
Heptachlor
Dieldrin
Dieldrin, Aldrin
Endrin, DDT
Lindane, Aldrin
DDT, PCNB
PCNB
PCNB
DDT
Dieldrin
Dieldrin
DDT
Lindane
Aldrin
Bacteria
Arthrobacter
Bacillus
Clostridium
Escherichia
Hydrogenomonas
Klebsiella
Micrococcus
Proteus
Pseudomonas spp.
Pseudomonas spp.
Pseudomonas
Unidentified
Unidentified
Actinomycetes
Nocardia
Streptomyces
Fungi
Aspergil lus
Fusarium
Mucor
Trichoderma
Yeast
Saccharomyces
Algae
Chlamydomonas
Chlorella and Dunaliella
-------
Bourquin (20) has reported extensively on microorganims,
chiefly soil and aquatic, which can partially degrade chlorinated
hydrocarbon pesticides in various environments (Table 33).
Beneckea and Caulobacter have been predominately represented by
marine or estuarine genera. It should be noted that microbial
degradation, which is probably the major natural mode of pesticide
reduction in the environment,is most often incomplete and results
in metabolites which may or may not exhibit toxic or mutagenic
characteristics. The degradation of DDT to DDE or ODD, for
example, results in products which can be bioaccumulated and create
lasting negative impacts.
Microbes growing on organics leaving pulp and paper mills are
nitrogen-fixing Azotobacter and Klebsiella (153) and the yeasts
Rhodotorula, Hansenula, and Pichia. It is indicated that yeasts
can remove resins from kraft mill effluents. Holladay et al.
(64) report Bacillus, Stapholococcus, Pseudomonas, Citrobacter,
Proteus, and Escherichia coli in association with weak ammoniacal
liquors from the coal-coking process.
102
-------
SECTION IV
SITE STUDIES
INTRODUCTION
In compiling and reviewing information for Section III, the
project staff became aware of various biodegradation techniques
being employed to treat problematic and/or large quantities of
industrial organic materials. This fourth section includes
detailed site studies on four biological treatment systems
handling industrial organic materials. Each study contains infor-
mation on:
Waste identification
Treatment system construction and design
Operations (parameters measured and methods)
Treatment efficiency
Economics.
The site selection process took place in four steps, outlined
below and discussed in the following paragraphs.
Step 1: Review literature and contact various sources for
study site suggestions and information
Step 2: Establish site selection criteria
Step 3: Use site selection criteria to determine appli-
cability of biological process(es) to this study
Step 4: Present and finalize selected sites with the EPA.
To determine the biodegradation techniques used for treating
industrial organic materials in 1977, SCS Engineers chose to
incorporate an initial literature search followed by personal
contact with individuals familiar with current biological treat-
ment techniques. These contacts included:
• State, provincial, and national governing bodies in both
the United States and Canada
• Equipment and hardware manufacturers
• Engineering consulting and design firms
103
-------
• Private industry
0 Institutes and societies
t Universities and colleges.
This step one search identified 19 potential study sites.
Site selection criteria were developed to assist both the
EPA and SCS Engineers in determining the site applicable to the
goals of the project. The site selection criteria were:
• Cooperation and applicability to project goals
• Geographic location
• Variety of organic materials treated
• Availability of system data
- Influent, effluent, and sludge waste streams
- Design
- Operation
- Costs: capital, operational, and maintenance-
Four sites which best satisfied these criteria were chosen
as representative of biological treatment techniques for organic
materials. These sites are described in detail in the following
pages .
104
-------
GULF COAST WASTE DISPOSAL AUTHORITY (GCWDA)
40-ACRE INDUSTRIAL WASTE TREATMENT FACILITY
TEXAS CITY, TEXAS
INTRODUCTION
The Gulf Coast Waste Disposal Authority (GCWDA) 40-Acre
facility consists of a series of lagoons biologically treating
raw and primary treated petrochemical and industrial wastewaters.
The waste streams were chosen by GCWDA for their amenability to
biological treatment and their ability to supply required
nutrients for biological degradation. The lagoons have a surface
area of 50.6 ha (125-ac) and treat a flow of 50,000 to 57,000 m /
day (13 to 15 MGD). Maximum possible retention time in the system
is 21 days. The biological lagoon series is as follows: anaero-
bic, limited aerobic, aerobic, and faculative lagoon wastewater
biodegradation. Figure 12 shows the arrangement of the lagoons:
Various problems are encountered in the conventional bio-
logical treatment of industrial and especially petrochemical
wastewaters. Difficulties include (65):
• Elevated temperatures which are detrimental to micro-
organism flocculation and separation
• Surfactants causing foaming problems
• Synthetic organic constituents inhibitory to nitrifiers,
protozoa, and flocculating organisms
• Varying qualities and quantities of organic wastes
discharged from a large petrochemical complex resulting
in nonequilibrium conditions.
To help combat these potential problems, the designers of
the 40-Acre facility proposed a system with large volume and long
treatment retention time. The large volume of this lagoon system
allows absorption of major waste quality changes without signi-
ficantly altering the bulk quality of the system contents. The
large surface area permits cooling to ambient temperatures.
Anaerobic treatment helps to stabilize problem materials such as
surfactants and reduce oxygen demand before aerobic treatment.
In addition, the open lagoon system provides an environment in
which photosynthetic bacteria and algae may proliferate. Near
the lagoon surface, aerobic bacteria may utilize surface entrained
105
-------
o
CT)
1 Emergency Holding Basin
2 Equalization Basin
3 Anaerobic Lagoons
4 Limited Aeration Basin
5 Aerated Stabilization Basins
6 Facultative Basins
7- Undeveloped Area for Future Facultative Basins
8 Hurricane Levee Pump Discharge Canal
9 Office and Laboratory Building
10 Swan Lake
Figure 12. GCWDA 40-Acre facility layout.
-------
and photosythetical1y produced oxygen to aerobically stabilize
organic wastes and oxidize inorganics such as sulfides.
History
The GCWDA is a public authority formed by the Texas State
Legislature in September 1969 to participate in industrial waste
treatment. On May 29, 1971, the Texas Water Quality Board (TWQB)
issued a Waste Control Order to the GCWDA to build and operate a
waste treatment facility at Texas City, Texas. Design engineering
was completed in 1971, construction began in early 1972, and initial
operation commenced in 1974.
There has been only one major system modification at the
facility since the initial construction. In February 1976, the
addition of 14 aerators converted the southernmost anaerobic
lagoon to a limited aeration lagoon.
Location
The 40-Acre facility is located approximately 56 km (35 mi)
southeast of Houston and 1.6 km (1 mi) south of Texas City,
which is 0.8 km (1/2 mi) from Galveston Bay and 0.4 km (1/4 mi)
from Swan Lake. Figure 13 shows the location of the facility,
which is located on the unrelieved flat Gulf Coast plain. The
area immediately surrounding the facility is a combination of
tideland and marshland. The soil is comprised of silty clay
materials.
Regional Characteristics
Petrochemical-related industries are numerous in the
Houston-Texas City area. This region contributes 30 percent of
the total United States petrochemical output (51). Economic
reasons for growth of the industry in this area include the
availability of sea transport and the location of 75 percent of
United States petroleum reserves within easy reach. Additional
factors include an abundance of water needed to meet industrial
demand and ease of pipeline construction on and under the flat
terrain.
The climate is humid and subtropical. Temperatures are
moderated by winds from the Gulf of Mexico, producing mild win-
ters. The location is, therefore, ideal for a large lagoon
treatment system. Rainfall is abundant, averaging 122 cm (48-in)
per year, and dry periods are rare (159). Evapotranspiration
averages between 107 and 114 cm (42 and 44 in) annually (150).
107
-------
o
oo
Figure 13. Location of GCWDA 40-Acre facility.
-------
WASTEWATER IDENTIFICATION
Sources
Three companies currently supply the wastewater influents to
the GCWDA 40-Acre treatment facility (Figure 14). The number
and types of waste streams and the monitoring data available
have varied during the past operation of the facility. Figure 15
summarizes the waste streams that were treated at 40-Acre from
January 1975 to March 1977.
Discharger 1--
Discharger 1 generates two major waste streams identified
as diluted and concentrated at the Texas City petrochemical plant
and provides primary treatment for both. In-plant waste streams
which make up Influent A are mixed and physically cleaned of deb-
ris at a junction box. Caustic may be added at this point if
necessary. Influent A then flows into two parallel center-feed,
27.4 m (90-ft) diameter primary clarifiers. After clarification,
the supernatant is pumped 4.8 km (3 mi) to the 40-Acre facility.
Influent BI flows into a skimmer unit where flotables are
removed. The waste stream is then pumped to an Off Plant
Disposal Area (OPDA) maintained by Discharger 1 and located
adjacent to the 40-Acre facility (Figure 14). The OPDA consists
of long-retention-time (up to one year) facultative lagoons for
the stabilization of the high organic content of the wastewater.
The effluent from the OPDA (Influent B) is transported to the
40-Acre facility for further treatment.
On October 25, 1976, pumping of Influent B] to the OPDA was
suspended and instead the wastewater was pumped directly to the
40-Acre facility anaerobic lagoons. Various odoriferous mer-
captan compounds were generated in the lagoons. This had not
previously occurred in the 40-Acre anaerobic lagoons when
influent B was treated. The odors led to the termination of
direct pumping of Influent BI to 40-Acre and reactivation of the
OPDA on March 24, 1977. Scientists from GCWDA and Discharger 1
are currently attempting to identify and isolate the problem
compounds.
Characteristics — Following is a description and characteri-
zation of the three waste streams from Discharger 1 transported
to the 40-Acre facility.
4 3
Flow of Influent A averages between 3.4 to 4.2 x 10 m /day
(9 to 11 MGD) with a pH of approximately 9. Temperature
fluctuates between 30 and 45°C. Tables 34 and 35 summarize data
on Influent A constituent concentrations average loading values,
109
-------
SCHARGER 1
Figure 14 . Location of industries supplying influent to
40-Acre facility.
-------
1975
1976
1977
INFLUENT A
INFLUENT B
INFLUENT B
INFLUENT C
INFLUENT D
F M
M J J
A
i
S
i
o
I
N
i
D
J
i
M
i
A
i
M
i
A
I
S
i
O
I
N D
J
i
F M
Figure 15. Historical representation of waste streams entering
the GCWDA 40-Acre treatment facility.
-------
TABLE 34. CHARACTERIZATION OF INFLUENT A (mg/O
ro
Parameter
TOC
COD
BOD
TSS
VSS
TDS
Chloride
Sulfide
Phosphorus
Fl uori de
TKN
1
Average
265
903
404
141
60
5352
2607
75.3
15.7
2.62
79.8
975
Ra
208
658
283
61
36
3387
1617
54.0
1 .55
2.47
19.1
nge
- 388
-1349
- 581
- 254
- 90
-6869
-3295
-109.9
- 36.6
- 2.97
-156.2
1
Average
255
910
467
99
46
3687
81 .9
4.12
1 .01
9.43
976
Range
205
766
381
56
29
2553
46.4
1.46
0.127
2.39
- 282
-1129
- 609
- 151
- 87
-4443
-118.7
- 9.31
- 2.84
- 23.1
1
Average
316
1141
498
164
65
51 .7
7.05
26.1
977*
Range
229 - 367
795 -1315
288 - 678
129 - 198
50 - 76
47.1 -59.3
4.06 -9.04
19.1 -33.7
* Average of Jan-Mar 1977
-------
TABLE 35. CHARACTERIZATION OF INFLUENT A
LOADING TO THE 40-ACRE FACILITY
OJ
Parameter
TOC
con
BOD
VSS
TDS
Chloride
Sulfide
Phosphorus
Fluoride
TKN
Average (1b/
kg/day day)
9864
33545
15136
2223
197727
96227
2795
591
100
2968
(21746)
(73954)
(33369)
(4901)
(435913)
(212144)
(6162)
(1303)
(220)
(6543)
1975
Standard
Deviation
2635
7185
3434
626
33330
16511
776
454
23
1910
Total
kg/yr
3594181
12209727
5510045
808318
72156000
35103227
1025363
215772
36500
1089181
Average (lb/
kg/day day)
9336
33263
17168
1682
139318
3009
154
36
336
(20582)
(73332)
(37849)
(3708)
(307144)
(6634)
(340)
(80)
(741)
1976
Standard
Deviation
934
4704
3044
522
33883
1034
68
27
231
Total
kg/yr
3406545
12473045
6261272
614727
50851136
1094863
56682
13364
123727
-------
respectively. The specific volatile organics identified in the
waste stream are (74):
Methanol
Ethanol
Isopropanol
Acetaldehyde
Acetone
Methyl ethyl ketone
Benzene
Ethylene glycol
Acetic acid .
Influent BI is characterized by a flow of less than 5.7 x
10 m3/day (1.5 MGD) and a high organic concentration, averaging
20,000 mg/£ COD. In addition to the volatile organics present in
Influent A, the concentrated waste stream contains (74):
Prop ionic acid
Butyric acid
Pentanol
Cr-aldehydes
C5-acids
Cc-alcohols
D
Phenol
Butyl ethers
Propyl ethers
Methyl isobutyl ketone
C-jg-18 alcohols
Formate.
Table 36 summarizes the average monthly concentration and
loading values for Influent B, .
Effluent from the OPDA (Influent B) enters the 40-Acre3
facility at ambient temperature; flows average 3.79 x 10 m /day
(1.0 MGD). The complex organics of Influent B, are oxidized in
the OPDA into simpler volatile acids and ketones, acetone,
methyl ethyl ketone, and methyl isobutyl ketone. COD values in
the effluent average 1,500 mg/£. The increased sulfide concen-
tration in the OPDA effluent is an indicator of sulfate utili-
zation as an inorganic oxygen source. Tables 37 and 38 illus-
trate yearly concentration and loading values, respectively.
Influent C, from Discharger 2, is characterized by a flow
averaging 1.14 x 1O4 x 1 O4 m3/day (3.0 MGD) and a pH of approxi-
mately 8. The waste stream has a high organic loading: BOD 9409
and COD 16,318 kg/day (20,743 and 35,975 Ib/day). Th$ raw waste
stream requires pretreatment to remove potentially disruptive
cyanide before transportation to 40-Acres. Tables 39 and 40
show concentration and loading values for Influent C.
Influent D is the result of the collection of water runoff
from a phosphate fertilizer manufacturing plant. Although the
flow of 6.4 x 102 m3/day (0.17 MGD) is not continuous, it averages
280 days a year. The low pH of this waste stream (approximately
2 to 4) is assimilated well when combined with the higher pH and
volume of Influents A, B, and C. Characteristics of the waste
114
-------
TABLE 36. CHARACTERIZATION OF INFLUENT B
1
Average
Daily
Standard
Parameter
TOC
COD
NH3-N
Total N
S°
so4
P°
Concentration
(mg/£)
4869
20568
1.36
203
0.413
24.8
136
Deviation
2367
12669
0.
80.
0.
9.
59.
453
3
294
496
2
Loadinn
kg/day
13418
47000,
6.5
641
0.9
59
405
Standard
(lb/day)Deviation
(29581
(103617)
(14.3)
(1413)
(2.0
(130)
(893)
) 3583
22698
1.6
476
0.5
54
206
Yearly*
Loading
kg/year
4904545
17227272
2356
234545
326
21455
148181
*Extrapolated from 6 months data.
-------
TABLE 37. CHARACTERIZATION OF INFLUENT B (mg/i)
Parameter
TOC
COD
BOD
TSS
VSS
TDS
Chi ori de
Sulfide
Phosphorus
Oil & grease
Phenol
NH3-N
Chromi urn
Average
613
1769
765
100
70
6740
1657
11.4
48.2
5.8
2.36
* 31 .3
2.51
1975
1976
Range
205
598
309
45
27
3387
966
2.2
18.4
2.5
0.79
13
1 .58
- 953
- 2599
- 1243
- 137
- 101
- 8263
- 2238
- 39.7
- 68.0
- 12.7
- 8.6
50
- 3.5
Average
419
1253
623
38
24
2850
743
9.3
17.2
4.1
0.76
8.08
2.68
Range
203
614
285
14
9
2138
574
0.3
7.7
1 .4
0.44
4.31
1 .0
- 1067
- 3370
- 1825
77
48
- 4127
- 1064
- 19.2
- 54.0
- 11 .0
- 1 .15
- 12.35
- 3.85
-------
TABLE 38. CHARACTERIZATION OF INFLUENT B LOADING VALUES (kg/day)
Parameter
TOC
COD
BOD
TSS
VSS
TDS
CT
S
P
Oil and grease
Phenol
NH3-N
Chromium
1975
Average lb/ Standard
kg/day day Deviation
3314 (7306)
1000 (2205)
4286 (9449)
532 (1173)
377 (831)
35477 (78213)
8168 (18007)
41 (90)
273 (602)
45 (99)
12 (26)
145 (320)
10 (22)
2204
6332
3021
336
240
20666
3951
32
181
59
14
77
7
kg/year
1199227
3515090
1551954
194227
137727
1287727
2616681
139500
141410
167545
3945
5777
1976
Average lb/ Standard
kg/day day Deviation
1173 (2586)
3550 (7826)
1768 (3898)
109 (240)
68 (150)
5509 (12145)
1436 (3166)
23 (51)
50 (110)
10 (22)
1.9 (4.2)
21 (46)
6.8 (15)
1324
4187
2241
113
73
3311
844
24
64
9
1.4
14
3.6
kg/year
428136
1304363
646848
39939
25090
1995954
519818
8485
17903
4136
711
7818
2473
-------
TABLE 39. CHARACTERIZATION OF INFLUENT C (mgA)
oo
Parameters
TOC
COD
BOD
TSS
VSS
TDS
Cl"
po
NHa-N
TKN
Oil and grease
Phenol
Fl uoride
Chromi urn
i
Average
430
1050
584
24
13
5520
1217
5.73
121 .8
134.5
2.32
0.78
0.55
1.25
1975
Ran
282 -
774 -
406 -
16 -
8 -
1249 -
1079 -
0.47 -
40.1 -
73.0 -
0.7 -
0.45 -
0.8 -
0.056-
1976
ge
694
1353
715
39
18
7838
1618
13.0
335
259.2
5.5
1 .8
1.9
2.06
Average
446
1163
682
33
15
5878
1185
0.37
98.4
118.4
2.1
0.86
0.15
0.92
Range
295 -
853 -
534 -
17 -
9 -
3980 -
825 -
0.02 -
32.0 -1
44.7 -2
1 .0 -
0.31 -
0.059-
0.47 -
651
1558
920
87
28
8719
1745
1 .39
96.6
12.1
4.9
1 .4
0.56
3.15
-------
TABLE 40. CHARACTERIZATION OF INFLUENT C LOADING VALUES (kg/year)
Parameter
TOC
COD
BOD
TSS
VSS
TDS
Cl"
P°
NH3-N
TKN
Oil and grease
Phenol
Fluoride
Chromium
1975
Average lb/ Standard
kg/day day Deviation
4636 (10220) 1506
11227 (24751) 2395
6227 (13728) 1429
436 (961) 517
140 (309) 40
30413 (67049)34763
12782 (28179) 1007
59 (130) 45
1229 (2709) 581
1501 (3309) 671
25 (55) 16
8 (18) 2.9
13.4(30) 3.9
5 (11) 10
1976
Average lb/ Standard
kg/year kg/day day Deviation kg/year
1549277 6455 (14230) 3482 2363973
3746033 16266 (35860) 7883 4877781
2077031 9394 (20710) 3837 3124757
138978 446 (983) 245 162564
45193 208 (459) 73 7495
20340234 83837 (184829)38673 30614904
3933245 16665 (36740) 6319 6102695
16832 5 (11) 5 1713
406784 1347 (2970) 626 495695
413168 1769 (3900) 1488 652320
8511 32 (71) 24 11222
2606 13 (29) 9 4664
40830 2.3(5.1) 2.7 855
701 12 (26) 9 4754
-------
stream are low organic content and high phosphorus and nitrogen
content. Tables 41 and 42 show the characteristic concentration
and loading values for Influent D.
Treatabil i t.y of Uastewater
There are certain requirements for the successful biological
treatment of industrial wastewaters. These are:
• Wastewater constituents in a form amenable to biodegra-
dati on
• Wastewater temperature in the 4 to 40 C range
• pH between 6 and 9
• Adequate nutrients available for biological metabolism
and eel 1 synthesi s
• Suppression of toxic or inhibitory materials through
removal, dilution, or inactivation .
In initial studies on the wastewater from the Texas City
petrochemical plant, engineers at Dicharger 1 determined that the
wastewaters were amenable to biodegradation, and with pretreatment
and nutrient addition, the wastewater satisfied the above mentioned
criteria.
Typical treatment of petrochemical wastewater involves aerobic
biological systems, in particular, activated sludge and aerated
stabilization processes. The high waste temperatures and high
oxygen demand rates of petrochemical wastewater require additional
expenditures to aerate the system and dispose of produced bio-
logical solids. Concern over these problems led engineers to
investigate possible anaerobic treatment of petrochemical waste-
waters. Anaerobic treatment is advantageous in areas with warm,
mild climates and land available for large lagoons needed for
anaerobic stabilization. The advantages and disadvantages of
anaerobic treatment, as determined by Discharger 1, are shown
in Table 43.
Three anaerobic treatment processes were selected Jor study:
• Anaerobic contact digester
• Anaerobic trickling filter
• Anaerobi c 1agoon.
The characteristics of these three systems, all first tested
in bench-scale, are shown in Table 44.
Anaerobic biodegradation of materials takes place in two
stages: (1) organic reduction to volatile acids, and (2) methano-
genesis of the volatile acids. Organic material in both the
anaerobic contact digester and trickling filter showed degradation
120
-------
TABLE 41. CHARACTERIZATION OF INFLUENT D (mg/fc)
Parameters
TOC
COD
BOD
TSS
VSS
TDS
Cl~
P
Sulfide
NH3-N
Fl uori de
1
Average
41 .
137.
16.
28.
12.
7056.
698.
909.
374.
306.
19.
62
67
346
69
68
6
44
88
66
13
91
975
Range
17.6
88.2
1 .5
18.8
6.25
5606
520
623
223
95
6.4
-
- 2
- 90
-
- 21
92
77
.5
62
.5
1
Average
3
11
5.
1 .
9.
29.
1
- 7890
- 900
- 11
- 5
50
71
- 546
- 31
.6
56
4.
55
3.
566.
490.
1
5.
3
1
7
3
03
1
9
1
3
1
1
4
06
1
9
03
1976
Range
19
67.4
4
16
8.3
3593
425
2022
260
10.5
50
- 192
14
- 48.7
23
-10152
-733.3
- 1530
- 1350
- 21 .9
-------
TABLE 42. CHARACTERIZATION OF INFLUENT D LOADING VALUES (kg/year)
ro
IN3
Parameter
TOC
COD
BOD
TSS
VSS
TDS
Cl~
P
S
NH3-N
Fluoride
1975
Average 1 b/Standard
kg/day dayDeviation
30
96
12
52
9
4870
484
624
247
199
13
(66)
(2120
(26)
(115)
(20)
(10737)1
(1067)
(1376)
(545)
(439)
(29)
18.8
48
22
82
3.3
284
138
248
80
143
8.6
kg/year
10804
34863
4305
7420
2988
2229032
176463
227770
9008
72219
4862
1976
Average lb/ Standard
kg/day dayDeviation
21
67
5.8
17
10
3288
327
351
288
9.3
(46)
(148)
(13)
(37)
(22)
(7249)
(722)
(774)
(635)
(21.)
12.4
41.8
3
11.1
6.1
1749
130
414
195
4.3
kg/year
7649
24473
2111
6375
3682
2114929
190742
128134
105762
3404
-------
TABLE 43. TREATMENT CONSIDERATIONS AT GCWDA 40-ACRE PLANT(66)
I. Advantages of Anaerobic Processes
A. No aeration equipment is required for organic reduction, Associated
capital, power, and maintenance costs are avoided. System loading
Is not limited by oxygen transfer.
B. Cellular material is produced in lower quantity and more stable form.
Savings in nutrients and in flocculants, equipment, and labor costs for
biomass dewatering and final disposal can be realized.
C. Some problem organic chemicals difficult to degrade aerobically will
degrade anaerbbically.
D. The oxygen in nitrate and sulfate ions can be utilized for organic
oxidation.
E. Methane in off-gas potentially can-be used for heating or in odor
control by incineration.
F. The anaerobic system can operate at temperatures at which a flocculant
aerobic system experiences biomass separation difficulties-
II, Potential Problems with Anaerobic Processes
A. High temperatures are needed1 for maximum, rates.
B. High biomass concentration is required for reasonable rates at short
retention times.
C. Regeneration time for methane bacteria is long (2 to ]] days at 37°C),
thereby requiring long solids retention and acclimation times.
D. Methanogenic microorganisms are reportedly more sensitive to shock
loads, toxic materials, and environmental conditions,
E. Effluents low in BOD (<50 mg/l) with good aesthetic properties are
difficult to produce.
F. Produced gases are odorous if released.
123
-------
TABLE 44. SYSTEMS STUDIED FOR APPLICATION AT 40-ACRE (66)
Description
Flow pattern
Biosolids level
Metabolic pathways
Retention time
Gas collection
Submerged Filter
Rock or gravel
packed column
Plug flow
High biomass
through attached
growths
Fermentation and
anaerobic
respiration
Contact Digester Open Lagoon
1 to 3 days
Normally collected
Temperature control Not normally
practiced
Completely mixed
vessel
Backmixed
High biomass
through settling
and return
Fermentation
and anaerobic
respiration
Basin with con-
siderable
stratification
Some wind and
wave mixing,
thermal turn-
overs
Low suspended
solids, bottom
sludge layer
Fermentation,
anaerobic
respiration,
sulfur oxidation,
photosynthesis,
some aerobic
respiration
10 to 100 days
Gas is released,
although a
plastic covering
with peripheral
collection files
is possible
Usually practiced Unfeasible unless
covered and
insulated
1 to 10 days
Collected
124
-------
to volatile acids. However, methane production was inadequate in
both cases, because of (1) inadequate retention time for generation
of methanogenic bacteria, or (2) volatile acid or sulfide concen-
trations inhibiting the system. The anaerobic lagoon did not
show these complications.
The most promising system, the anaerobic lagoon, was devel-
oped into a pilot-scale demonstration unit to optimize the process
and provide economic and design data adaptable for a large-scale
plant. Pilot-scale aerobic treatment studies were made of the
effluent from the anaerobic unit. These studies provided infor-
mation for designing and estimating the cost of a total treatment
plant combining the roughing anaerobic treatment with the
polishing aerobic treatment. Facultative lagoons added after
the aerobic treatment provide a long retention time and large
area for solids separation and subsequent storage and anaerobic
decomposition of the solids. Figure 16 shows the final demon-
stration system schematic.
GCWDA made an agreement with Dischargers 1 and 2 to construct
and operate a full-scale biological treatment system to treat the
petrochemical wastewater.
For biological treatment of wastewater, biodegradable
organics and nutrients need to have a BOD/N/P weight ratio of
approximately 100/5/1 (58). The combined values of Influents A,
B, and C and their relationship to required nutrients (Table 45)
show the combined waste streams to be deficient in phosphorus.
GCWDA, to negate phosphorus nutrient addition, contracted with
Discharger 3 to treat the runoff water from the letter's phosphate
fertilizer storage area. The inclusion of this waste stream
satisfied the 40-Acre phosphorus requirements (Table 46).
REGULATORY REQUIREMENTS
Influents and effluent from the GCWDA 40-Acre facility are
under the jurisdication of the National Pollution Discharge
Elimination System (NPDES), as administered by the Texas Water
Quality Board (TWQB). Monitoring requirements for Dischargers
1 and 2 are shown in Table 47 and for Discharger 3 in Table 48.
In addition, there are specific influent limitations covered
under the permit (Table 49).
TREATMENT SYSTEM CONSTRUCTION AND DESIGN
The GCWDA 40-Acre treatment system consists of:
• pH adjustment (HC1 )
• Nutrient addition (H3P04, NH3)
t Emergency spill diversion
25
-------
Anaerobic Lagoons
(10 - 15 day retention)
(1,703 m3)
Aerated Stabilization
(2-3 day retention)
(114 m3)
Facultative Lagoons
(1.2 to 2 day retentions)
(79 m3)
PO
cr>
Feed:
Neutralized
Nutrients Added
BOD-^ 700
COD~ 1300
Anaerobic Lagoon
Cross Section
1 . rj 111
15 m
3.7 m
(30.5 m)
Fi gure 16.
Anaerobic-aerobic demonstration system for determining waste treatment
design at~40-Acre (66)
-------
TABLE 45. COMBINED INFLUENT A, B, AND C LOADING VALUES*
AND THEIR RELATIONSHIP TO REQUIRED NUTRIENTS
Influent A
Influent B
Influent C
Total
BOD
17000
1770
9390
28160
COD
33000
3540
16280
52820
Phosphorus
154
50
4.5
209
Nitrogen
336
23
1770
2129
Required BOD/N/P weight ratio 100/5/1
Available BOD/N/P weight ratio 100/7.5/0.7
Average kg/day
127
-------
TABLE 46. COMBINED INFLUENT A, B, C, AND D LOADING VALUES*
AND THEIR RELATIONSHIP TO REQUIRED NUTRIENTS
BOD COD Phosphorus Nitrogen
Infl
Infl
Infl
Infl
uent
uent
uent
uent
A
B
C
D
17000
1770
9390
5. 9
33000
3540
16280
68
150
50
4.5
350
336
23
1770
288
Total 28166 52888 555 2417
Required BOD/N/P weight ratio 100/5/1
Available BOD/N/P weight ratio 100/8.5/2
Average kg/day 1976 data
128
-------
TABLE 47. DISCHARGERS 1 AND 2 INFLUENT MONITORING REQUIREMENTS
Characteristic
BODr
COD
TSS
Oil and Grease
NH3-N
Chromium
Phenols
R-C1
Phosphorus
Fluoride
Cyanide
Mercury
Lead
Arsenic
TKN
Flow
Temp.
PH
Measurement Frequency^
Daily
Daily
Daily
3/v/eek
Daily
I/week
2/week
I/week
2/month
2/month
2/month
2/month
2/month
2/month
2/month
Continuous
Continuous
Continuous
Sample Type
24-hr.
24-hr.
24-hr.
Grab
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
24-hr.
Record
Record
Record
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
129
-------
TABLE 48. DISCHARGER 3 INFLUENT MONITORING REQUIREMENTS
Characteristic
BOO,
COD
TSS
Oil and Grease
MH3-N
Chromium
Phenols
R-C1
Phosphorus
Fluoride
Cyanide
Mercury
Lead
Arsenic
TKN
Flow
Temp.
pH
Measurement
Frequency
Daily
Daily
Daily
3/week
Daily
I/week
N/A
N/A
2/mdnth
2/month
1/3 months
1/3 months
1/3 months
1/3 months
1/3 months
Daily
Daily
Daily
Sample Type
24-hr
24-hr
24-hr
Grab
24-hr
24-hr
N/A
N/A
24-hr,
24-hr.
24-hr,
24-hr.
24-hr.
24-hr.
24-hr.
Estimated
Grab
Grab
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
composite
130
-------
TABLE 49. DISCHARGERS 1, 2, AND 3 INFLUENT LIMITATIONS IN
KG/DAY (LB/DAY) EFFECTIVE JULY 1, 1977
Discharge 1 Discharge 2 Discharge 3
Characteristic Daily avg. Daily max. Daily avg. Daily max. Daily avg. Daily max.
Total chromium 15.3 (33.7) 30.7 (6.77) 1.1 (2.4) 2.3 (5.1) 0.20 (0.44) 0.40 (0-88)
Aliphatic chlori- 0.33 (0.72) 0.66 (1.45) 2.0 (4.4) 4.0 (8.8) N/A N/A
nate hydrocarbon
Cyanide N/A N/A 4.6 (10.1) 9.3 (20.5) N/A N/A
Fluoride N/A N/A N/A N/A 15* 30*
N/A - Not available
* mq/i
-------
t Equalization
• Anaerobic, limited aerobic, aerobic and facultative
biological treatment.
Figure 17 shows a schematic diagram of the facility's
layout and Table 50 the dimensions and retentions of the basins.
The facility design was based upon an extensive laboratory
and pilot study of anaerobic treatment of petrochemical waste-
waters. The study was conducted by Discharger 1 during the late
1960's and early 1970's; a summary of the design findings is
presented later in this chapter. The treatment system was
designed for a primary treated petrochemical wastewater with
maximum values as follows: flow, 5.1 x 1 C)4 m3/day (13 MGD);
loading, 59,000 kg/day BOD (130,072 Ib/day); and 118,000 kg/day
(260,145 Ig/day) COD.
Construction
The facility basins were excavated by balance cut and fill.
Basin slopes are two horizontal units for each vertical unit.
To control wave erosion of the embankment all earthen basins are
lined with 10 cm (4-in) of concrete from the crest of the slope
to 61 cm (3-ft) below the water surface. The impermeability of
the clay-rich soil made complete lining of the basins unnecessary.
The berms are topped by a roadway, approximately 3.6 m (12-ft)
wide. The entire facility is enclosed by a 1.8 m (6-ft) high
chain link fence topped by three strands of barbed wire- The
area is lighted by 30 utility pole-mounted high intensity lamps.
The facility operates continuously.
The four waste streams currently treated at the facility
(Influents A, B, C, and D) are transported there in individual
pipelines. Influent enters the facility at two points (Figure 17)
Influents A, B, and C at influent point 1; Influent D, because of
its high sulfur content, enters at influent point 2, bypassing
the anaerobic lagoons. Influent flow measurements are determined
by venturi (differential pressure) meters inserted in the pipe-
lines.
Chemicals for pH adjustment (HC1) and nutrient addition
(H^P04 and NH3)are stored in tanks adjacent to influent point 1
( Figure 17).
Figure 18 shows the distribution piping within the facility.
The flexibility of this system allows various retention periods
and treatment schemes, depending upon influent loading and com-
position. Basin interconnect piping is low-head corrugated metal
drainage pipe with a protective coating. Liquor flow through
the system is gravitational. There are no provisions for
returning settled biomass from the facultative lagoons to the
aerated stabli1ization basins.
132
-------
CO
CO
PH ADJUSTMENT
AND
NUTRIENT
ADDITION
INFLUENT
POINT » 2
AERATED STABILIZATION
BASIN
/
/
OFFICE AND
LABORATORY
AERATED STABILIZATION
BASIN
FLU
INT
i
3-
•*-/-
/
NC1
AS
ENT
»1
k
' N
r
1-
(
f
[N
^
^
k J-
-x
N
I
1
V
i
/
Sj
s \
\
s
\
Jf*
(X-
N
ANAEROBIC LAGOON
n^
EQUALIZATION
- BASIN
.
ANAEROBIC LAGOON
uj
LIMITED AERATION BASIN
1
t*-
\
_rl
~tf
M--
\L
(
,c-—
y^-
/
1 i
> s
-
1 I
— x — ^y
1
S
[f I
•- -/•• - "\
/
1 • - •• ••
"~" INCOMPLETE
FACULTATIVE
LAGOON
4 A
FACULTATIVE
LAGOON
1
FACULTATIVE
LAGOON
j^i: 1
Figure 17. GCWDA 40-Acre facility layout: schematic diagram.
-------
TABLE 50. 40-ACRE BASIN DIMENSIONS
AND RETENTION
Basin
Number
Emergency 1
spill
Equalization 1
Anaerobic
Limit 1
aeration
Aerated 2
s t a b i 1 i z a t i o n
Facultative 3
Dimensions in
meters (ft)*
188x56x4.0
(618x184x13)
188x56x4.0
(618x184x13)
430x154x4.0
(1410x506x13)
372x188x4.0
(1220x618x13)
430x154x4.0
(1410x506x13)
248x125x2.4
(815x410x8)
445x166x2.6
(1460x545x9)
Capaci ty
103 m3 (mgl)
42 (11)
42 (11)
265 (70)
265 (70)
76 (20)
189 (50)
Retention
days+
5
1 .5
3.7
Total basin acreage - 50.6 ha (125 ac)
Length x width x depth.
At maximum design flow: 51,100 m3/D (13.5 MGD)
134
-------
INFLUENT
POINT
CO
(Jl
Figure 18. 40-Acre distribution piping.
-------
Sampling platforms are located at each of the anaerobic
lagoons and at the limited aeration lagoon. Wastewater testing
and maintenance duties are handled in the laboratory and office
building located at the facility.
The facility uses the Ashbrook Mechanical Surface Aerator-
High Speed (MSAH) Model 75/900 (75 hp, 900 rpm) for oxygen
transfer and maintenance of solids suspension. Figure 19 shows
a schematic of the aerator, and Table 51 gives the aerator
characteristics. There are 50 such aerators at the facility:
14 in the limited aeration basin and 18 in each aerated stabili-
zation basin. Each aerator is moored to wooden pilings by cables.
Summary of Discharger 1 Study into Petrochemical Wastewater
Treatment
During the late 1960's and early 1970's, Discharger 1 made
extensive laboratory and pilot study into the biological treat-
ment of petrochemical wastewater. A system design was used that
incorporated anaerobic, aerated stabilization and facultative
treatment. A summary of the findings follows; a more complete
discussion of the research that preceded the design is included
in Reference 66.
Anaerobic Lagoons--
The anaerobic lagoons provide waste equalization and cooling
as well as removal of inhibitory material and a portion of
influent oxygen-demanding materials.
The anaerobic degradation of petrochemical wastewater
organics was found to vary both with temperature and volumetric
loading rate (mass of organics applied/unit volume-time).
Degradation was greatest at warm temperatures and light loading
rates and decreased with either a temperature drop or a loading
increase. Figure 20 shows COD removal as a function of volumetric
loading and temperature. The area under the COD percentage
removal line represents temperature and loading conditions that
can be expected to have COD removal values of that level or -
greater. For example, at a COD loading of 160 kg COD/1,000 m
(10 lb/1,000 ft3) and a wastewater temperature of 300C, a COD
removal of 55 percent or greater is expected. The retention
time required to arrive at these removal values can be computed
from the following equation: *
Retention (days) = Influent concentration (ma/a)
J ' Desired loading (mg/Jl/day)
Percent BOD removal in the anaerobic lagoon showed a significant
correlation with percent COD removal (Figure 21).
The depth of the anaerobic lagoon was found to have an
effect upon sulfide concentration in the lagoon; effects of
136
-------
LIFTING EYES FOR HANDLING ASSEMBLED UNIT.
TEFC ( TOTALLY ENCLOSED FAN COOLED) MOTOR
WATER TIGHT CONDUIT BOX (CAST)
MORSE MORFLEX RA'DIAL COUPLING
ELEVATED MOTOR SUPPORT
DEFLECTOR
CO
FLOAT IS EQUIPPED WITH FOUR
(4) MOORING EYES.
MOORING CABLE, SHOWING CORRECT METhCC
OF ATTACHING WIRE ROPE CLAMPS.
POLYUHETHANE FOAM FILLED FIBREGLASS FLOAT
WELDED STEEL FRAME .
F GOODRICH GUTLESS BEARING ON
SHAFT COATED WITH TEFLON
IMPREGNATED CERAMIC.
IMPELLER
CORE
STRAIGHTENING VANES
WATER LEVEL
Fi gure 19.
Ashbrook Mechanical Surface Aerator - High Speed (MSAH)
76 horsepower/900 rpm approximate weight - 2023 kg.
-------
TABLE 51. ASHBROOK MSAH 75/900 CHARACTERISTICS
Oxygen transfer factor:
2
Impingement diameter:
3
Pumpi ng rate:
Induced flow rate:4
Diameter of surface area
influence:5
1.3 kg 02/HP-HR
13.1 m (43 ft)
108.8 m3/min (28,740 gal/min)
438.7 m3/min (115,900 gal/min)
122.8 m (403 ft)
Diameter of effective mixing: 38.4 m (126 ft)
1 Under standard conditions of 1 atm,
20°C
The impingement diameter describes the spray pattern of the
pumped liquid. This water is distributed through the
atmosphere radially and horizontally in the form of countless
small droplets and thin liquid envelopes for oxygen entrain-
ment. The kinetics of the discharged liquid are utilized
to move surface water away from the aerator for efficient
mixing.
3 The pumping rate of an ASHBROOK MSAH Mechanical Aerator is
amount of liquid pumped through the pumping chamber.
the
The induced flow rate of an ASHBROOK MSAH Mechanical Aerator
is the total influenced fluid which is pumped directly and/or
kept in motion indirectly.
The diameter of surface area influence describes the general
periphery of the upper liquid level containing dissolved
oxygen. The diameter was calculted usinq 2.2 hp per 1,000
f c i *••
^ Of lc
m
agoon surface area
The diameter of effective mixing is determined by assuming
a horsepower value per unit volume of the basin. iTii s value
can vary from 3.53 hp to 35.3 hp per 1,000 m3 Of basin
depending upon the density of the suspended solids.
The diameter of effective mixing was calculated using 17.7
hp per 1 ,000 m3.
138
-------
480
oo
25 20
Temperafure, °C
15
10
Figure 20- COD removal as a function of loading and temperature.
-------
80
o
o
Q
O
ca
70 -
60
50 -
40
30 -
20
10 -
COD Removal, %
Figure 21. Relationship between BOD and COD removal
140
-------
*
J
60
50
40
30
20
10
A-189 reactor
Q-1.8 and 3.6 m experi-
mental facility
O -20820 reactor (effec-
tive depth computed as
volume/surface area)
0.6 0.9 1.2 1.5 1.8 2.1 2.4
Lagoon Depth, TO
2.7
3.0
3*4
10
3.7
8
J-
30 -g
o
u
20 S
IS)
Figure 22. Effect of lagoon depth on COD removal and suicide level.
-------
depth on both COD removal and sulfide concentration are shown
in Figure 22. Overall COD removal changed by only 11 percent
with a fourfold increase in depth, whereas the surface sulfide
level increased by a factor of two.
Aerated Stabilization--
Aerated stabilization was chosen to provide the additional
treatment required for the anaerobic effluent. The aerated
stabilization process is a high-rate lagooning operation employing
a low concentration of nonf1occulent bacteria synthesized during
biooxidation of the organics and discharged with the effluent.
Given a proper environment and lack of toxicants, the performance
of an aerated stabilization process is limited by one of two
factors. If the system is not operated at a positive oxygen
level, removal is dependent upon the quantity of oxygen supplied.
If oxygen is maintained above some level where performance is
independent of oxygen concentration, the limiting mechanism is
retention time for bacterial growth and resulting assimilation
of waste products. If the rate of liquid flow through the
reactor and resulting detention time is less than the time
required for stabilization, only a portion of the waste will be
removed. As the detention time becomes greater, near equilibrium
stabilization is reached.
In order to determine the limiting oxygen level, a study
was performed on a pilot aerated stabilization unit in which the
oxygen level was controlled. At 1 mg/Jl residual DO, the unit
became dark and odorous. This condition was suggested to be
due to incomplete conversion of sulfides, resulting in end
products such as sulfite, thiosulfate or elemental sulfur (66).
A DO residual of 1.5 mg/£ was found to be necessary to avoid
odor problems and to maintain acceptable BOD and COD removals
(70 and 60 percent, respectively).
The pilot unit was aerated continuously for up to 8 days
to determine the optimum retention time for aerated stabilization
(Figure 23). A three-day aeration period was found to be
sufficient.
Facultative Lagoons--
The biosolids produced by the aerated stabilization lagoon
are nonflocculent and consequently settle at a slow rate.
Facultative lagoons were selected to provide a long retention
time and a large area for solids separation, as well as for
subsequent storage and anaerobic decomposition of the solids.
After two days retention.removal of approximately 60 percent
of the applied volatile and suspended solids from the wastewater
stream was observed (Figure 24).
Two pilot-scale facultative lagoons were operated for a
231-day test period. During this time, 1,065 kg (2,348 Ib) of
total suspended solids (TSS) and 879 kg (1,938 Ib) of volatile
142
-------
CO
300 -
11/1/70 Sample
o
0
u
12/H/70 Sample
I
1 1/24/70 Sample
(spill in jyifem)
.
1
cf
O
150
- 300 -
COD
o
O
50
?
200
c
O
t-u 100,
OL 0
0123456789
Da/>
L o
12/18/70 Sample
COD
BOD
1 1 1 1 1 1
1 J
012345 6789
Days
Figure 23, Effect of additional aeration on aerated stabilization effluent.
-------
-F=-
-p.
Total suspended solids
Volatile suspended solids
120 160 200
Influent Suspended Solids, mg/l
Figure 24. Relationship of lagoon feed and effluent solids levels
-------
suspended solids (VSS) were removed from the effluent and stored
in the lagoons. At the end of this operational period, solids
remaining in the lagoon system were composed of 467 kg (1,030 Ib)
of TSS and 39 kg (86 Ib) of VSS. A material balance proved that
degradation of total and volatile suspended solids amounted to
50 and 70 percent, respectively.
OPERATIONAL INFORMATION
The 40-Acre treatment facility is monitored daily at
sampling stations located within the lagoon system. This
enables the GCWDA operators to select a treatment scheme to
best handle the incoming waste streams. For example, a waste-
water with a low organic content will not require the total
aeration capabilities of the aerated stabilization basins.
Individual aeration units can be shut off, or a basin may be
bypassed, reducing maintenance and energy costs. Table 52 shows
the variety of operational modes which have been used at the
facility from February 1975 to May 1977.
Sampling and monitoring stations within the lagoon system
are located so that each of the four biological processes
(anaerobic, limited aeration, aerated stabilization, and facul-
tative) can be monitored. Sampling platforms are located in
each of the anaerobic lagoons and in the limited aeration basin
(Figure 25). Samples from the aerated stabilization basins are
taken from a skiff. The facultative lagoon effluent is monitored
at the outfall station.
Flow proportional composite samplers, with associated
refrigeration units, are located so that samples can be drawn
from influent and effluent streams and from the influent to the
aerated stabilization basins (Figure 25). Grab samples are
used to analyze waste in the aerated stabilization basins.
The following pages describe the parameters measured in
the individual basins and the representative values thereof.
The monitoring data for the facultative lagoons are included
in the "Treatment Efficiency" section of this report.
Anaerobic Lagoons
The anaerobic lagoons were used to treat Influents A, B,
and D until February 1976. At that time the southern anaerobic
lagoon was converted to a limited aeration basin with the
addition of 14 surface aerators. The two other anaerobic lagoons
remained idle until October 1976, when Influent BI was transferred
to the lagoon. Table 53 summarizes the anaerobic lagoon effluent
data for 1975.
145
-------
TABLE 52. GCWDA 40-ACRE OPERATIONAL
MODES AS OF FEBRUARY 1975
February 1975 - March 1975
Influents A, B, and D into equalization basin (EQB) into #2
Anaerobic Basin into splitter box. Influent C enters at splitter
box. Parallel flow into the Aerated Stabilization Basin (ASB)
into #3 Facultative to #2 Facultative and out.
April 1975 - May 1975
Flow same as above. Parallel flow to ASB into #3 Faculta-
tive and out.
June 1975 - February 1976
Influents A, B, and D direct to #1 Anaerobic Basin to #1
ASB into #2 ASB. Influent C enters splitter box directly into
#2 ASB (bypassing #1 ASB) and combined flow exists to #3 Facul-
tative and out.
February 1976 - June 1976
Influents A, B, and D into EQB into Limited Aeration Basin
(LAB) into splitter box mixing with Influent C. Parallel flow
into ASB into #2. Facultative and out. Approximately 6 aerators
off in #2 ASB in April and May.
July 1976 - October 1976
Flow same as above until after splitter box and then directly
into #2 ASB and then to #2 Facultative and out.
November 1976 - December 1976
Influents A and D to EQB, Influent B directly to LAB, Influ-
2nt Bn directly to #1 Anaerobic oh to #2 Anaerobic (no effluent).
LAB effluent to splitter box mixing with Influent C and then paral
lei to the ASB to #2 Facultative and then out. Approximately 9
aerators off in #1 and #2 ASB. •
146
-------
f
1 Sampling platforms 2 Composite samples
Figure 25. Location of monitoring hardware.
-------
TABLE 53,
40-ACRE FACILITY:
(1975 Data*)
ANAEROBIC LAGOON
Parameter
TOC
COD
BOD
TSS
VSS
Alkalinity
Volatile
acids
Po
NH3-N
Sulfide
S04
mg/l
295
971
520
34
17
878
166
17.2
30.3
5.73
57.9
Range
208- 420
668-1222
297- 946
19- 78
9- 37
643-1135
68- 290
2- 34
18- 46
0.4- 14.7
32- 112
kg/day
12,478
41,123
22,108
1,470
717
36,746
7,149
744
1,284
249
2,395
(lb/day)
(27,509)
(90,660)
(48,740)
(3,241)
(1,581)
(81,011)
(15,760)
(1,640)
(2,831)
(549)
(5,280)
pH average 9.3, range 9.0 - 9.7
Temperature average 29°C, range 21 - 35 C
Average of daily reports for the entire year
148
-------
TABLE 54. 40-ACRE FACILITY:
LIMITED AERATION BASIN EFFLUENT QUALITY
(1976)
Parameter
TOC
COD
BOD
TSS
VSS
pO
NH3-N
Sulfide
S04
D.O.
cr
TDS
TKN
mg/l
101
396
104
157
127
3.99
12.6
0.18
67
1.7
2265
4707
19.8
Range
67- 146
286- 562
63- 201
101- 277
82- 214
1.62- 14.82
2.15- 20
0.04- 0.28
38- 104
0.9- 3.2
1231-3179
3112-5924
6.3- 28.7
kg/day
3,371
14,429
3,561
5,479
4,495
109
513
1.0
2,658
64
81,479
173,422
324
(lb/day)
(7,432)
(31,810)
(7,851)
(12,079)
(9,910)
(240)
(1,131)
(2.0)
(5,860)
(141)
(179,630)
(382,330)
(714)
pH average 7.9, range 7.6 - 8.2
149
-------
TABLE 55. AERATED STABILIZATION BASINS
F/M RATIOS FROM 1975-1976
Date
Feb 1975
March
Apri 1
May
June
Ju ly
Aug
Sept
Oct
Nov
Dec
Jan 1976
Feb
Mar
April
May
June
Ju ly
Aug
Sept
Oct
Nov
Dec
#1 Basin
0.74
0.44
0.84
1 .20
1 .46
5.03
1 .75
1 .22
0.93
0.95
0.69
0.84
1.15
0.45
0.50
0.62
0.48
( no sampl ing)
( no sampl i ng )
#2 Basin Mode of Operation
0.82 [
0.48
0.64
Paral 1 el
1 .03 L
0.69
1 .07
0.55
0.46
0.39
0.32
0.44
0.58
0.65
0.41
0.39
0.47
0.52
1.11
0.80
0.93
0.68
0.65
0.46
Series with Influent
entering #2 basin
" Paral lei
#2 basin only
Paral 1 el
150
-------
TABLE 56. 40-ACRE FACILITY:
AERATED STABILIZATION BASINS (ASB) MONITORING DATA
(1975)
Parameter
TOC
COD
BOD
TSS
VSS
SS
NH3-N
Po
D.O.
D.O. Uptake
ma/ 1
112
498
.
222
176
15.
41.
13.
4.
6.
t
36
5
8
0
1
3
ASB
Range
78-185
390-652
7-174
108-321
71-263
0.4- 69.0
20- 82.3
0.32- 25
1.3 - 7.3
2.6 - 16.3
#1
ASB #2
kg/day
5
24
3
11
8
1
2
,271
,031
,130
,294
,963
,220
,159
939
204
331
(Ib/day)
(11,621)
(52,979)
(6,900)
(24,899)
(19,760)
(2,690)
(4,760)
(2,070)
(450)
(730)
mg/l
98
451
23
231
170
16.9
43.4
11 .7
5.5
3.6
Range
62-160
388-651
8- 81
171-341
116-245
2.2 - 81
24- 70.6
0.25- 21 .8
3.5 - 7.6
1.8 - 7.6
kg/day
5,012
21 ,723
3,275
26,080
8,677
975
2,214
612
279
181
(Ib/day)
(11
(47
(7,
(57
(19
(2,
(4,
(1,
(61
,050)
,891)
220)
,497)
,130)
150)
881)
349)
5)
(399)
pH: avg 8.1 range 7.9 - 8.3
Temperature: avg: 26 range 19-32
pH avg: 8.1 range 7.9 - 8.3
Temperature avg: 25 range 18-31
-------
TABLE 57. 40-ACRE FACILITY: AERATED STABILIZATION BASINS (ASB) MONITORING DATA
(1976)
ASB #1
Parameter
TOC
COD*
BOD
TSS
VSS
SS
NH3-N
Po
D.O.
D.O. Uptake
mg/t
77.5
192.3
22.15
184.28
151.05
13.39
19.13
1.00
6.14
4.73
Range
42
156
11
103
74
1
4
0
3
1
.6-120.4
.6-255.6
.9- 45.9
-253
.9-229.4
.9- 23.4
.8- 36.4
.21- 1.94
.6- 8.0
.5- 9.4
kg/day
3,493
8,664
998
8,301
6,804
603
862
45
277
213
(Ib/day)
(7,700)
(19,101)
(2,200)
(18,301)
(15,000)
(1,330)
(1,900)
(99)
(611)
(470)
mg/l
72
180
18
209
155
13
33
1
5
3
.18
.9
.4
.6
.2
.94
,72
.29
.73
.95
ASB #2
Range
42.9- 99
143 -213
9.9- 26
136.9-298
100.9-211
4.1- 28
11.3- 64
0.25- 8
5.25- 7
2.04- 5
.6
.9
.7
.4
.6
.6
.6
.36
.36
kg/day
3,311
8,301
844
9,616
7,121
640
1,547
59
263
181
(Ib/day)
(7,300)
(18,301)
(1,861)
(21,200)
(15,699)
(1,411)
(3,411)
(130)
(580)
(399)
pH ayg: 8.0 range 7.7-8.5
pH avg: 8.1 range 7.9-8.4
* Five day, COD
-------
CJ1
CO
TABLE 58. TWQB DAILY AVERAGE EFFLUENT LOADING DISCHARGE LIMITATIONS:
8/75-7/77, AND THE CORRESPONDING MONTHLY 40-ACRE EFFLUENT
LOADING DISCHARGE FOR MARCH 1975-APRIL 1977
Effluent Characteristic in kg/day^
TWOB EFFI IIFNT
1 rVV^U l_ 1 1 1_ U l_! 1 1
LIMITATIONS
August 1975
September
October
November
December
January 1976
February
March
April
May
June
July
August
September
October
November
December
January 1977
February
March
BOD5
2953 (6510)
919 (2026)
610 (1345)
915 (2017)
981 (2163)
982 (2165)
967 (2132)
1068 (2355)
1096 (2416)
756 (1667)
559 (1232)
497 (1096)
652 (1437)
594 (1310)
827 (1823)
939 (2070)
944 (2081)
1422 (3135)
3971 (8755)
1823 (4019)
856 (1887)
COD
23627 (52089)
16825 (37093)
14076 (31032)
14012 (30891)
15903 (35060)
14003 (30871)
14856 (32752)
15556 (34295)
14019 (30907)
12268 (27046)
9804 (21614)
11432 (25203)
12611 (27802)
11560 (25485)
11368 (25062)
10827 (23869)
14690 (32386)
18246 (40226)
29876 (65865)
18943 (41762)
14398 (31742)
TSS
6497 (14323)
3790 (8356)
2161 (4764)
2985 (6581)
4234 (9334)
3359 (7405)
4935 (10880)
3813 (8406)
2827 (6232)
2268 (5000)
1372 (3025)
1823 (4019)
2935 (6471)
2924 (6446)
2480 (5467)
2620 (5776)
4512 (9947)
6220 (13712)
10570 (23303
6382 (14070)
4496 (9912)
(Ib/day)
Oil &
Grease
297 (655)
40 (88)
55 (121)
29 (64)
26 (57)
41 (90)
35 (77)
31 (68)
44 (97)
54 (119)
76 (168)
133 (293)
109 (240)
78 (172)
89 (196)
54 (119)
89 (196)
172 (379)
159 (350)
106 (234)
134 (295)
Ammonia-N
2859 (6303)
2814 (6203)
1834 (4043)
2778 (6124)
3397 (7489)
2945 (6493)
1445 (3208)
1312 (2892)
2452 (5406)
2047 (4513)
1483 (3269)
1082 (2385)
1169 (2577)
2106 (4643)
2046 (5511)
2788 (6146)
2440 (5379)
2198 (4846)
1833 (4041)
2401 (5293)
2532 (5582)
Mean
1096 (2357)
14764 (32549) 3835 (8455)
78 (172) 2156 (4753)
-------
TABLE 59. TWQB EFFLUENT LOADING
DISCHARGE LIMITATIONS EFFECTIVE JULY 1, 1977
Effluent
Characteristic
BOD5
COD
TSS
Oil and Grease
Ammonia-N
Discharge Limitations in kg/day (Ib/dav)
Daily Average Daily Maximum
1,769 (3,900)
20,639 (45,501)
2,722 (6,001)
297 (655)
594 (1,310)
3,983 (8,781)
31,298 (69,000)
5,897 (13,000)
593 (1,307)
1,188 (2,619)
154
-------
Limited Aeration Basin
Aerators were added to one anaerobic basin to help eliminate
the sulfide odors that had been a problem in the anaerobic
lagoons. The aerators maintain dissolved oxygen levels in the
basin between 1 and 2 mg/£. Table 54 summarizes the limited
aeration basin effluent data for 1976.
Aerated Stabilization Basins
Grab samples are used to analyze constituents in the aeration
basins. Dissolved oxygen levels are maintained above 2 mg/£.
In the basins, the food-to-micoorganism (F/M) ratio averages
0.34 kg BOD/kg MLSS (0.34 Ib BOD/lb MLSS) when the waste flow
is split and passed in parallel through the two basins. The F/M
ratios in the basins for 1975-76 are summarized in Table 55. To
determine the operational status of the basins for a specific
month, values from this summary are compared with the modes in
Table 52. Tables 56 and 57 show the values of operational
parameters for 1975 and 1976, respectively.
In addition to the waste parameters shown in Tables 56 and
57, the amounts of ammonia and phosphorus are also monitored
in the plant effluent. When there are not enough nutrients
in the effluent, chemical nutrients, such as NH~ and FLPO,, are
added. However, since Influents C and D have been included in
the waste stream, nutrient addition has not been required.
TREATMENT EFFICIENCY
The first portion of this discussion will present the ability
of the treatment facility to meet effluent limitations set by
the Texas Water Quality Board (TWQB). The second portion will
present the overall efficiency of the system in terms of
wastewater constituent removal.
Effluent standards for the facility are set by the TWQB, in
accordance with the NPDES program. Effluent limitations are set
in loading values (kg/day) and not in concentration values (mg/£).
Table 58 shows the effluent loading limitations in force from
August 1975 through July 1977 and the corresponding effluent
loading values for August 1975 through March 1977. Table 59
shows the effluent limitations that took effect on July 1, 1977.
In certain instances, the effluent did not meet established
effluent loading discharge limitations. For example, in
January 1977 the limitations were exceeded by the BOD5, COD, and
ammonia-N effluent loading discharge values. An evaluation of the
temporary excesses indicated that the removal capabilities of
the biological system had been exceeded at this time and that
specific influent loading limits would be necessary if the
system is to meet regulatory requirements. However, the facility
155
-------
TABLE 60. AVERAGE WASTEWATER CONSTITUENT
REMOVAL EFFICIENCY - MAY 1975 THROUGH DECEMBER 1976
Wastewater
Characteristic
TOC
COD
BOD
TSS
VSS
TDS
po
NH3-N
S°
Phenol
Cl"
No. of Months
for Which Data
% Redu
75
75
96
33
-23
- 4
70
-69
-128
10
-9
c t i o n
.8
.8
.3
.0
.5
.24
.7
.5
.8
.6
8
Range
59
65
91
-33
-171
-21
35
-241
-234
-165
-34
.9-
.7-
.5-
.8-
.9-
. 1-
.4-
.5-
.5--
.2-
.5-
81
78
98
69
42
9
98
42
73
97
7
.7
.6
.1
.0
.8
.9
.0
.6
.1
.3
.7
is Available
20
20
20
20
20
12
20
20
8
17
8
Negative values indicate increase in the effluent loading
over the influent loading.
156
-------
is not a static system. The retention and aeration period and
treatment processes are not fixed and can be varied by the oper-
ators. Consequently, although the capabilities were exceede-d
during a certain period, it cannot be concluded that system
removal limitations were reached; loading limitations require
further study.
Removal efficiency levels for various wastewater constituents
are maintained by modifying the treatment schemes, for example,
series vs. parallel flow in the aeration basins, and amount of
aeration. These operational modes should be referred to (see
Table 52) when reviewing the treatment efficiencies shown in
the following tables. Table 60 summarizes the average treatment
efficiencies for May 1975 through December 1976. It should be
noted that in certain instances, loading data for all influent
constituents are not available. Table 60, therefore, includes
indications of the number of months for which data were available.
In reviewing the values in Table 60, it should be noted that
removals of TOC, COD, and BOD are constant, while reductions of
other constituents fluctuate widely. The main objective of
biological treatment systems is the removal of oxygen-demanding
materials. The absence of highly fluctuating TOC, COD, and BOD
values indicates a stable and we!1-acclimated microbial population
in the various treatment steps. In addition, the COD removal of
76 percent reflects the beneficial effects of the long retention
time of the 40-Acre system. Many organic petrochemical wastewater
constituents, especially complex synthetic organic compounds,
are consequently recorded as COD. These organics are the prin-
cipal reason why smaller scale, high-rate systems treating petro-
chemical wastewater show such poor TOC removal efficiencies.
The long retention characteristic of the 40-Acre system allows
the plant biota sufficient time to degrade the resistant-organic
molecules .
The apparent increases in certain wastewater constituents
are, however, somewhat misleading. For example, Influent A is
not tested for NhL-N because concentrations are quite low.., ^
However, with a high flow of the wastewater, up to 40 x 10 m /
day (10.5 MGD), the loading values of even a low concentration
will be significant. This premise is also applicable to the
apparent increase in effluent oil and grease loading over the
influent loading.
Conditions in the facultative lagoons are conducive to algal
growth. Increases in the loading in the effluent, when compared
to influent loading values, are due primarily to the presence of
algae.
TDS and Cl" ion concentrations are not appreciably affected
by the 40-Acre system. Influent vs. effluent TDS and Cl loadings
157
-------
TABLE 61 . MAJOR ASSUMPTIONS OF THE CONSTRUCTION
COST ESTIMATE
1. Earthwork slopes are two horizontal units for each vertical
unit.
2. Piling is required under all major structures.
3. A Gulf Coast location is assumed.
4. All earthen basins are lined with four inches of concrete from
the top of the slope to two feet below the water surface unless
otherwise noted.
5. Basin interconnect piping is low-head corrugated metal drain-
age pipe with protective coating.
6. All costs adjusted to 1976 dollars.
158
-------
TABLE 62. CONSTRUCTION COST ESTIMATE:
ANAEROBIC-AERATED STABILIZATION SYSTEM
53 x 103 m3/fcay Flow (14 MGD) , 65 ha (160 ac)
Neutrali zation
Structural $ 46,200
Mixing 19,530
Reagent Storage 63,840
pH Control 25,200
C1arificat ion
Structural 259,560
Mechanical Equipment 123,900
Anaerobic Ponds
Earthwork 685,650
Concrete Liner 82,530
Aerobic Basin
Earthwork 439,950
Concrete Liner 68,880
Aeration Equipment 940,800
Electrical Support 179,550
Facultative Ponds
Earthwork 284,550
Concrete Liner 124,110
Piping 351,540
Instrumentation 117,600
Building and Lab Equipment 107,100
Site Preparation 103,110
Land at $l,000/acre 160.000
Subtotal $4,183,600
Construction Contingency 433 ,716
Construction Cost $4,617,316
159
-------
remain relatively equal or vary slightly. Effluent increases
could be due to chemical reactions within the system, and
decreases could be due to chemical complexes .in the sludge floe.
ECONOMIC EVALUATION
The GCWDA 40-Acre facility was constructed in 1974 at a
cost of $5.5 million, with financial assistance from Pollution
Control Revenue Bonds. The system was designed for simplicity
of operation and with few major structural components (e.g.,
sludge dewatering equipment) so as to save on both annual
operating and maintenance costs. However, the system is land
intensive, covering 160 ac. The 1976 operation and maintenance
costs totaled $550,000; 60 percent was funded by Discharger
the remainder by Discharger 2. Power requirements, including aera
tion demands, totaled $350,000; labor costs, $135,000; and other
supplies, $30-40,000.
There were chemical cost savings when Influent D was added
to the facility influent. Phosphoric acid and hydrochloric
acid addition costs had approached 10 percent of O&M costs; the
low pH (2-3) and high phosphorus content of Influent D made the
addition of these acids unnecessary.
An economic comparison between activated sludge and anaero-
bic-aerated and stabilization-facultative systems is included in
Anaerobic Treatment of Synthetic Organic Wastes, by Hovious et al.
(66).Using the informationin this report and referring to
appropriate economic indices, construction costs (in 1976 dollars)
can be projected for a system similar to 40-Acre. This system
includes pH adjustment, primary clarification, anaerobic, aerated
stabilization, and facultative lagoons. Table 61 lists the
major assumptions of the construction cost estimate. The estimate
is shown in Table 62.
In 1976, the average influent and effluent BODt; loadings
were 26,101 kg/day (57,543 Ib/day), and 860 kg/day (1,896 Ib/day)
respectively, for a net BODs reduction of 25,241 kg/day (55,647
Ib/day). The 1976 operation and maintenance costs of $550,000
plus the annual amortization of $480,000 ($5.5 million over 20
years at 6 percent) yield a total annual cost of $1,030,000. The
40-Acre system cost per kilogram BOD. removed is $0.11*($10.ll/
Ib BOD.) . b
160
-------
GULF COAST WASTE DISPOSAL AUTHORITY (GCWDA)
WASHBURN TUNNEL INDUSTRIAL WASTE TREATMENT FACILITY
PASADENA, TEXAS
INTRODUCTION
The Gulf Coast Waste Disposal Authority (GCWDA) Washburn
Tunnel Facility, a large high-rate activated sludge plant in
Pasadena, Texas, is capable of processing about 2.1 x 1O5
m3/day (55 MGD). The 9.7 ha (24 ac)site includes primary treat-
ment facilities for barscreening and grit removal and primary
clarification. Nutrient addition, pH control, and cooling
towers are used to prepare the primary effluent for introduction
to the complete-mix aeration basins which are equipped with
mechanical surface aerators. Effluent from these basins is
passed into one of two secondary clarifiers, where a percentage
of the sludge is wasted to a filter press-incinerator installa-
tion, and the remainder is cycled back to the aeration basins.
Sludge centrifuges, and a control building, control systems,
and a minicomputer are also at the site. All clarification and
aeration basins have concrete walls and bottoms. Two spill
lagoons located at the east side of the plant are used only when
extremely toxic or concentrated wastes are accidently introduced
to the plant and must be diverted and re introduced slowly to
avoid system upset.
The plant treats six industrial waste streams and discharges
to the Houston Ship Channel. Presently, sludge is barged to an
off-site landfill but it will eventually be burned in a new
incinerator.
HISTORY
GCWDA participation in industrial waste treatment was
authorized under the statute creating the authority, adopted by
the Texas Legislature in September 1969. The letter of agreement
GCWDA signed in September 1970 with five industries was the
initial step in forming the first joint waste treatment facility
in the Gulf Coast area. Compatibility-treatability tests,
funded by the industrial participants, were used to determine if
the individual wastes could be combined in a single biological
treatment plant. In November 1970, the Texas Water Quality
Board approved the concept of joint treatment contingent upon
proof of waste compatibility and authorized GCWDA to proceed
with the project.
161
-------
Contracts between GCWDA and the industries were signed in
May 1973. Subsequently, $25 million in bonds were issued;
$12-1/2 million were to go to the purchase of an existing 1.7
x 105 m3/day (45 MGD) treatment plant. The contract also
stipulated that, following the bond sale and plant purchase,
GCWDA would become owner and operator of the facility. Under
the terms of the agreement, the participating industries con-
tracted to pay all bond amortization, maintenance and operating
costs, plus a management fee to the GCWDA in the amount of
$120,000 annually.
In 1973, an expansion program was begun which would provide
an additional biological train and sludge handling facility and
expand the plant capacity to 2.1 x 105m3/day (55 MGD). The total
cost of the expansion, $14 million, was financed by the remainder
of the original bond issue.
LOCATION
The Washburn Tunnel Facility is located in the city of
Pasadena on the east side of Houston, Texas (Figure 26). The
facility is on the southern shore of the Houston Ship Channel,
and the plant effluent is discharged to the channel. The
Vince Bayou is to the west of the facility and the Washburn
Tunnel (an automobile tunnel under the ship channel) is located
to the east (Figure 27).
REGIONAL CHARACTERISTICS
Refinery and petrochemical production and storage facilities
are the major industries of the area. This southeastern portion
of Texas contributes 30 percent of the total U.S. petrochemical
output. The ship canals and nearby Galveston Bay and Gulf of
Mexico provide excellent transportation routes for raw materials
and finished products. Crude oil from nearby petroleum reserves
in Texas, Oklahoma, and Louisiana is easily piped or trucked into
the area. The land is relatively flat, and underground pipelines
are easily installed and serviced.
The advantages cited above have made industrial property
adjacent to the ship canals a popular and relatively expensive
commodity. Because land costs are prohibitively high,w waste
treatment designers have avoided sprawling, land-intensive
lagoon treatment schemes. The Washburn Tunnel has a low
surface-to-volume ratio typical of process schemes consisting
of separate, deep basins. This has mandated the use of
innovative techniques for waste temperature control prior to
biological treatment.
162
-------
en
CO
Figure 26. Map of Houston, Texas and vicinity.
-------
Figure 27. Map of Washburn Tunnel.
164
-------
Temperatures in the Gulf Coast region of Texas are
moderated by coastal winds, with summer daily maximums in the
low thirties (degrees centigrade, Table 63). Rainfall is fairly
evenly distributed throughout the year, and the annual rainfall
exceeds average potential evapotranspiration. A large portion
of the rainfall occurs within short periods of time and results
in excessive runoff or local flooding. Relative humidity is
highest along the coast and decreases inland. According to
climatological data (113), the mean annual relative humidity at
noon, Central Standard Time, varies from approximately 60 percent
near the coast to around 35 percent in the West Texas desert
region. Recurring weather conditions limit to 60 percent
the possible total annual sunshine. Tropical cyclones
occasionally pass through the Texas coastal zone; high winds
and floodings, especially extreme tidal fluctuations near the
coast, cause a great deal of damage. Effects of the storms in
the vicinity of the Washburn Tunnel Facility are limited
primarily to wind or tornado damage with occasional flooding.
WASTE IDENTIFICATION
Sources
In 1976, four industries discharged aqueous waste streams
to the Washburn Tunnel Facility. One additional industry
discharged both aqueous and concentrated sludge waste streams.
The treatment plant influents are summarized below:
Source
Discharger 1
Discharger 2
Influent
A
B
Avg. Monthly Flow percent
10 m /day (MGD) Total Flow Description
127.8 (34)
10.4 (2.7)
Discharger 3
2.4 (0.63)
Discharger 4
0.4 (0.1)
76 Paper mill wastes
(black liquor)
6 Primary petrochemi-
cals; capacity for
benzene, toluene,
and xylene produc-
tion
1.5 Petrochemical pro-
ducts; capacity for
vinyl acetate pro-
duction by
acetylene process
.5 Petrochemical pro-
ducts; capacity for
butadiene produc-
tion (from butylenes)
165
-------
TABLE 63. TEMPERATURES IN THE GULF COAST REGION OF TEXAS.(159)
LATITUDE
LONGITUDE
IUVAT1ON (ground)
29' 39' K
BS' IT »
50 Foet
NORMALS, MEANS, AND EXTREMES
UOU3TOX, TEXAS
(ILLIAU P. HODBV AIRPORT
JJ
e
o
J
9
M t
A
J '
CT» A
S
0
N
D
r*
Temper* lure
Normal
g
65,5
71.7
78.0
91.1
92.1
92.0
89.1
92.3
71.1
65.4
79.0
j
f!
46.0
50.8
59.0
72.0
73.8
73.6
69.)
60.4
30.5
45.9
59.3
2
1
35.8
61.1
68.3
76.0
81.6
93.0
81.2
7«,2
71.4
60.8
53.7
69.2
Extremes
"HI
8i
KJ3
97
98
91
94
100
101
106
98
96
82
106
|
1962
1967
1963
1967
1963
196*
1962
1963
1962
1963
196*
AUG.
1962
o S
i-,
29
38
52
59
6*
64
50
18
32
IV
17
a
1963
1963
1962
1967
1964
1967
1967
1967
196*
1968
1963
JAN.
1961 +
S.
T3
Nona a
299
192
36
0
U
0
0
0
6
183
307
1396
Precipitation
•3
B
J
1.**
2.67
3.2*
».32
3.69
*.29
».27
4.26
1.77
3.96
4.36
43.93
1 *
1!
1U55
11.42
8.07
13.24
14.66
12.38
18.31
15.40
22.31
14.36
9.90
22.11
A)
1959
1937
1937
1969
1960
1942
19*5
1959
194V
1946
19*9
OCT.
1949
Minim u
month!
0.09
0.07
0.36
T
0.09
0.07
U.19
0.1*
T
0.19
0.78
I
j
195*
19S3
1937
19S7
193*
1962
1956*
1933
1952
19*9
1958
OCT.
1952*
i s
5.03
5.00
3.18
6.33
8.31
6.3*
13.63
3.62
10.25
7.89
4.19
15.65
a
1966
1957
1966
1969
1*60
1943
1943
1944
19*9
19*3
196*
AUG.
1»*S
Snow, Steal
3
S
36
0.2
T
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
T
0.4
g .
1 H
36
4.4
1.0
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.0
T
4.4
1
1960
1969
1961 +
FEB.
I960
H
.S •«
9 S
X .S
16
4.4
1.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
T
*e*
1
I960
1968
1961 +
FES.
1960
•a
X
(0
a
o
o
K
S
StBDdBfd
time ueed :
CENTRAL
91
82
86
87
99
an
87
*5
93
82
81
84
86
99
91
91
91
99
86
93
94
97
60
39
6}
61
19
59
60
52
60
6*
60
A3
62
69
65
6*
6*
65
68
69
66
Wind I
_>.
1 7
ll
17.1
12.7
11.0
11.7
10.2
9.9
8.*
9.1
9.8
11.2
11.1
10.8
ii
SSE
SSE
SSE
sse
J
SSF
SSF
ESE
ISF
SSE
SSE
Fule«t mill
1
*0
33
18
**
*0
34
11
in
13
3*
0
&
16
10
16
17
16
3*
16
11
14
31
34
1
1963
1969 +
1966+
1963
1964
1963
1961
19»7
1961
1968 +
AUG.
1961
.a
*s
JU
1
36
57
3*
72
74
70
66
71
50
62
:y cover
to vuBJet
si
SI
6.7
7.0
3.6
5.9
•>,!
5.4
*.7
"<<.»
6.7
6.2
Mften number of dty*
Sunriaa
lo
•unn«t
J
7
6
5
6
5
8
9
12
9
8
97
O,*o
5
13
7
17
17
15
12
10
8
5
126
I"
o
0
16
12
IB
7
9
a
9
9
13
ie
152
i!
* O
u-S
£°
10
e
8
8
9
9
9
7
e
10
103
0
if
11
I
«
0
0
n
n
n
0
o
0
•
1
Thwnde
?
4
7
10
9
1
t
39
•g
*
1
^
ft
j
J
6
t,2
Tempe
Max.
Tl
S?
§? 4
0
0
1
19
26
26
1 &
3
0
95
?1
o
0
0
0
0
0
•
aluretf
Mm.
•o
a ^
6
0
0
0
4
13
o
0 'and be
o
o
0
0
0
0
0
M»iDi* sod axtresev ID the above table are froa coaptrable exposures for perlodB through the current yosr except aa noted hereafter. Aanual extrenv* have been exceeded at other locations •« follows:
Ulgb««t te»per«ture 108 in August 1909; lowest temperature 5 lo January 1940 snd oerller; faeteet «ila of *tnd 84 froa Horthiwat In Uarcb 1926.
0 For record Aufuat I960 throujfb the
Note:
1 cm = 0.3937 in
oc = 5/9°F-17.77
1 Km = 0.62137 mi
-------
Source
Influent
Discharger 5
(Aqueous )
Avg. Monthly Flow
loV/day (MGD)
26.4 (7.0)
Percent
Total Flow
15.7
Description
Petrochemical pro-
ducts; capacity
for xylene pro-
duction from
reformate and
toluene dispropor-
tionation
Discharger 5
(S1udge)
0.34 (0.09)
.3
Source: 130.
All waste flows are piped to
outlying industrial sites.
the treatment plant facility from
The influents, except the aqueous influent from Discharger
5 (Influent F), enter the treatment plant at pretreatment and
primary treatment stages. The wastes are screened, processed
for grit, and passed through primary clarifiers before going to
the aeration basins. Influent F passes primary treatment and is
introduced directly to the aeration basin influent.
RAW WASTE
Characteristi cs
Tables 64 and 65 show the average 1976 concentrations and
loadings, respectively, for constituents in each of the six
identified waste streams. In compliance with the National
Pollutant Discharge Elimination System (NPDES), such measurements
are reported monthly to the treatment plant by each industry.
In 1976, Influent A contributed 76 percent of the total annual
flow, and contributed 90 and 76 percent, respectively, of the
total BO05 and COD loading. The highest average quantities of
oil and grease and phenols originated in Influent B, with aver-
age monthly loadings of 2,300.1 kg/day (5,071.7 Ib/day) and
567.7 kg/day (1,251.8 Ib/day), respectively. In terms of con-
centration, Influent B was highest in average phenol content
51.7 mg/£), while Influent C was highest in average oil and
grease content (556.9 mg/i). Influent D had the highest concen-
trations of BOD5 and COD, 1,045.5 and 15,568.3 mg/t, respectively,
Taking into account the percentage of total flow contributed by
each waste stream, the average combined waste stream temperature
is 38.2°C (100.8°F), the average pH 8.0. The average temperature
for the major source (Influent A) is 39°C (102.2°F). The pH
ranges from 1.8 for Influent C to 11.1 for Influent D. Acidic
and caustic materials have been neutralized as a result of the
167
-------
TABLE 64. 1976 SUMMARY - WASHBURN TUNNEL FACILITY: INFLUENT WASTES (mg/l)
Influent
Parameter
Flow ^ -,
(x 10 m /day)
(M6D)
PH
BOD5
TSS
COD
oo Color
NH3-N
TOC
CN-
F-
S-2
Cr
A
Average
127.8
(33.7)
8.2
367.8
831.3
1179.3
479.0
1.61
201.8
.1
.4
1.7
.02
Range
125.5-
132.0
7.3-
9.2
298-
502
689-
1046
995-
1345
417-
585
0.27-
3.66
166-
240
—
0.23-
0.84
0.18-
5.47
.01-
.04
Average
10.4
(2-7)
9.0
400.3
261.5
1460.6
215.0
71.1
150.2
0.6
19.0
16.6
1.3
B
Range
8.131-
12.5
7.7-
9:6
275-
616
95-
507
958-
2801
142-
385
27-
120
120-
177
0.11-
1.27
6.6-
38.9
0.46-
124
.34-
5.69
C
Average
2.404
(0.6)
1.8
89.8
111.3
2300.7
5575
12.3
288.9
—
1.1
.04
—
D
Range
2.1-
2.7
1.5-
2.0
48-
123
7-
604
987-
9325
1625-
9525
6.6-
29.7
219-
499
—
.8-
2.12
—
—
Average
0.93
(0.2)
11.1
1045.5
4205.7
15,568.3
520.0
18.3
1386.6
--
0.7
—
1.6
Range
.66-
1.26
9.8-
11.9
519-
2086
2554-
6760
4,446-
43,904
—
2.8-
27.9
935-
2146
—
0.5-
0.8
—
0.4-
4.3
E
Average
26.4
(7.0)
7.0
204.4
141.0
570.0
125.0
10.6
180.2
0.3
0.6
1.0
0.5
Range
20.1-
28.9
6.6-
7.2
134-
205
104-
169
387-
636
—
4-
15
119-
214
—
0.47-
0.77
—
0.2
0.7
Average
0.34
(0.09)
9.5
10.8
11,721.3
1092.5
40.0
~
470.2
0.2
1.7
1.0
0.1
F
Range
0.14-
0.63
8.7-
10.3
8-
15
6,771-
19,811
636-
1617
—
—
243-
1063
—
1.13-
2
—
—
-------
TABLE 64 (continued)
CTi
Influent
Parameter
OiG
'nenols
NC5-N
TKN
TCS
TF
A
Average Range
7.7 1.8-
26.1
1.8 0.43-
7.87
3.3
1.5
1550
0.9
B
Average Range
217.6 61-
447
51.7 25-
97
--
--
--
0.7 0.5-
0.8
C
Average Range
556.9 311-
1704
2.5 0.02-
28.23
--
..
--
0.1
D
Average Range Average
66.3
0.7
..
22.0
1335.8
0.3
E
Range
54-
80.5
0.05-
2.81
--
--
1100-
1633
--
F
Average Range
6.8 4-
12
0.05
--
16.5
404.3 215.
992
1.7
-------
TABLE 65. 1976 SIJMMARv - UASHBURN TUNNEL FACILITY: INFLUENT WASTES kq/dav (Ib/day)
Influent
F arampter
Flow
(xl03m3/day)
MGD
pH
Temp.
BOD5
TSS
COD
Color
NH3-N
TO:
CN"
r"
Average
127.818
(33.7)
8.2
39°C
47310.7
(104084)
105904.0
(232989)
150861.1
(331894)
61274.9
(134805)
201.1
(442.4)
25835.4
(56837.9)
<12.7
('•27.7)
58.6
(128.9)
A
Range
125.498-
131.959
7.3-
9.2
35.5-
41.10C
38031-
63216
87938-
134413
125554-
167932
53751-
73391
34-
452
21,734-
31030
--
29-
111
Average
10.391
(2.7)
9.0
42.2°C
4071
(8964)
2808.8
(6179.4)
15092.2
(33202.)
2258.1
(4967.8)
734.3
(1615.5)
1574.8
(3464.6)
6.0
(13.2)
195.9
(431)
B
Range Average
8.131- 2.404
12.469 (0.6)
7.7- 1.,°,
9.6
32.7- 41.6°C
48.9°C
3026- 210.9
5711 (464)
1050- 213.4
5621 (469.5)
8970- 4655.2
26252 (10241.4)
1279- 10738.3
3696 (23624.3)
332- 26.1
1384 (57.4)
1255- 673.4
2087 (1481.5)
0.86- <.23
15 (-.51)
63- 2.49
424 (5.48)
C
Range
2.108-
2.741
1.5-
2.0
36.1-
47.2°C
78.5-
297
16.3-
917
2113-
10961
3646-
17830
12-
53
506-
950
--
1.4-
4.1
1
Average
.931
(0.3)
11.1
32°C
898.6
(1977)
3736.2
(8220)
13023.8
(28652.4)
--
19.3
(42.5)
1164.3
(2561.5)
--
0.59
(1.3)
3
Range
.662-
1.264
9.8-
11.9
28.3-
39.4°C
479-
1511
2317-
5985
3592-
26685
--
2.7-
38
893-
1899
--
0.41-
0.91
1
Average
26.35
(6.9)
7.0
32.6°C
0.862
(1.9)
3821
(8406)
15119.7
(33263.3)
--
276.8
(609)
4878.2
(10732)
N.D.
15.5
(34)
E
Range
20.14-
28.88
6.6-
7.2
27.2-
37.7°C
3584-
6391
2079-
4850
10324-
19204
--
94-
386
3412-
5935
--
9.5-
20
F
Average
0.341
(0.09)
9.5
48°C
3.67
(8.07)
3971.6
(8737.5)
342
(752.4)
--
0.54
(1.19)
143.9
(316.6)
N.D.
0.54
(1.19)
Range
0.144-
0.625
8.7-
10.3
37.2-
62.8°C
1.41-
7.26
104f-
6831
126-
539
--
0.45-
1.54
47-
334
--
0.23-
0.9!
-------
iA5LE 65 (continued)
Influent
Parameter
S-2
Cr
Ov3
D'-.enols
NC3-N
TK'J
IDS
TP
Average
201.2
(442.6)
2.31
(5.08)
957.1
(2105.6)
236.2
(519.6)
414.1
(911)
183.3
(403)
19459.1
(42810)
115.7
(254.5)
A
Range
(MGD)
24-
687
1.22-
5.4
56-
3350
56-
1046
--
--
Average
193
(425
11
(25
2300
(5060
567
(1248
-
-
.4
-5)
.7
.7)
.1
.2)
.7
.9)
-
-
B
Range
(MGD)
3.6-
1574
3.2-
45
535-
4326
200-
973
--
--
C
Average Range
(MGD)
<0.091
(<0.20)
--
982.4 135-
(2161.3) 1443
5.7 0.045-
(12.5) 64
--
--
D
Average Range Average
(MGD)
1.
(3.
1.32 0.32- 12
(2.9) 3.8 (26
1787
(3931
1/J
(31
N.
--
45
2)
.1
.6)
.0
.2
-2)
D.
36053.9
(79319)
--
9
(20
.3
-5)
--
0.23
(0.51)
27
(59.4)
I
Range
(MGD)
3.2-
19
1140-
2346
1.36-
53
--
--
28436-
52238
--
F
Average
Rangt
(MGD)
N.D.
N.D.
1.91
(4.2)
N.D.
N.D.
--
147.6
(324.7)
N.D.
--
1.36-
2.27
--
--
--
45-
368
--
-------
combining of waste streams with extreme pH; the resultant pH
is in the acceptable range of biological waste treatment.
In many instances, N03-N and TKN were not monitored or
reported. However, for the constituents reported, the ratio of
biologically oxidizable carbon (BODs x 0.375): nitrogen:
total phosphorus is approximately 19,685.15 kg/day (43,405.8 lb/
day): 1,672.24 kg/day (3,687.3 Ib/day): 152.2 kg/day (335.6
Ib/day), or approximately 100:8.5:0.8. The percentage of
nutrients is somewhat low in relation to the calculated bio-
degradable carbon content, which may indicate that some nutrients
must be applied to the waste prior to biological treatment.
The ranges for cyanide, fluoride, sulfides, and chromium
indicate that these materials are highly variable in the waste
streams. Cyanide and fluoride are not present in levels which
could significantly impact biological populations in either
the treatment facility or receiving waters. Influent B had the
highest sulfide content, 16.6 up to 124 mg/£. Chromiurn,which was
also present in some wastes,could be a problem if not removed
prior to discharge.
The combined waste flow is also monitored by the Gulf Coast
Waste Disposal Authority at the influent points of the Washburn
Tunnel Facility. These data are filed monthly in compliance
with the NPDES Discharge Permit requirements. Table 66 lists
the average waste constituent concentrations for 1976, as derived
from the monthly reports. For comparison, the constituents in
the waste streams shown in Table 64 have been used to estimate
concentrations in the combined waste stream (correcting for
percent of total flow) and are also shown in Table 66. Average
waste loadings for 1976 have been calculated and are presented
in Table 67; total waste stream loadings from Table 65 are shown
for comparison. Differences between the average influent
measurements and the values derived from the individual waste
streams are probably due to error; any significant difference
due to other causes is probably masked by random variation.
The values for the influent/effluent report are taken at
the sampling station where the wastes are combined. As indica-
ted previously, Influents A, C, D, and F are passed through a
bar screen, grit chamber, and primary clarifiers befogs being
combined with the aqueous Influents B and E. Primary screening
and sedimentation result in the removal of settleable suspended
and some colloidal materials, while relatively little of the
dissolved organic or inorganic compounds are affected. It is
suggested that the total suspended' solids (TSS) and, to a
lesser extent, the total organic carbon (TOC) would be slightly
reduced at the influent sampling station.
172
-------
TABLE 66. 1976 INFLUENT SUMMARY - WASHBURN TUNNEL (mg/£)
Average from Influent/
Effluent Report
Flow x 103
PH
BOD
COO
TSS
0&6
Phenol
Sulfide
ON"
Mercury
TOC
Chromi um
Color
NH3-N
Fluoride
TKN
N03-N
Total-P
m3/day 169.832
(not reported)
338
1 ,199.
704
31 .6
3.9
1 .3
0.14
.0027
184
0.19
482
7.8
1 .5
(monthly average
not available)
(month ly average
not available)
(monthly average
not avai Table)
Sum of Individual Flows
(Table-52 )**
168.27 n.r.*
8.0
342
1 ,189
727
37.7 (1)
5.0 (1)
2.3 (1)
0.19 (2)
(6)
203
0.17 (1)
483
7.4 (1)
1 .6
4.6
2.6
0.81
n.r. number of waste streams (out of 6 total) for which
the monthly average level of the constituent was
not reported.
it
Corrected for percent of total flow.
173
-------
TABLE 67. 1976 INFLUENT SUMMARY - WASHBURN TUNNEL kg/day (Ib/day)
From influent/effluent
report
Flow 1.7
(45
pH
BOD
x 105m
MGD)
57,173
COD 202,344
TSS 1
O&G
Phenol
Sulfide
CN~
Mercury
TOC
Chromi urn
Color
NH3-N
Fluoride
19,077
5,315
663
203
24
<.20
31 ,254
27.4
81 ,702
1 ,329
253
3/day
(126,066)
(53,419)
(262,565)
(1 ,403)
(175)
(54)
(6.3)
(<0.05)
(8,251)
(7.2)
(21 ,569)
(351)
(67)
TKN (monthly average
not available)
NO~-N (monthly average
not available)
Total (monthly average
P not available)
Sum of individual flows
(Table 65 )
1.7 x 105m3/day (1 ) (n.r. )*
(45 MGD)
8.0 (18)
52,494 (115,749)
199,094 (439,002)
119,958 (264,507)
6,029 (1,592)(1)
824 (182)(1)
396 (87) (1)
<12.7 (28) (1)
(6)
34,270 (75,565)
27.4(60.4)(D
74,271 (3)
(163,768)
1,258 (2,774)
274 (604)
183.3 (404)
414.1 (913.1)
152.2 (335.6)
n.r. number of wastestreams monthly (out of 6 total)
for which the average level of the constituent
was not reported.
174
-------
Effluent limitations are specifically established for the
Washburn Tunnel Facility in the NPDES permit. Under the permit,
the Gulf Coast Waste Disposal Authority was authorized by the
state of Texas to discharge the wastes originating from speci-
fied sources to the Houston Ship Channel after a required level
of treatment is achieved. Table 68 shows the permissible
loading rates for various constituents in the Washburn Tunnel
effluent as specified in the NPDES permit effective through
June 1977. Limitations are expressed both as permissible month-
ly averages and maximum permissible loadings per day for any one
day of the month.
Waste parameters discussed so far are those for which the
facility has reported monthly averages, i.e., more than one
measurement per month is made. However, as indicated, there
are a number of constituents, particularly metals, that are
measured once a month and reported as maximum loadings or
concentrations. Averages and ranges of these monthly maximums
for 1976 are shown in Table 69. Comparison of the average
constituent levels in the plant effluent with the standards
specified in the NPDES gives an indication of the required
treatment efficiency or percent removal that must be accomplished
by the Washburn Tunnel Facility. Results of this comparison are
shown in Table 70. Of the parameters measured, BOD, COD, TSS,
oil and grease, sulfides, cyanide, zinc, and titanium require
some degree of removal to meet permit reauirements. Cadmium
ranged in excess of the permissible maximum only one month in
the year. The rates at which other compounds, including arsenic,
barium, boron, cobalt, copper, lead, manganese, molybdenum,
nickel, selenium, and silver were found to be released indicated
no substantial reduction required before discharge to the
Houston Ship Channel.
Amenability to Biological Treatment
The following characteristics of the raw influent waste
could adversely affect biological treatment:
9 Elevated temperatures
• Presence of oil and grease and phenolic compounds
® High COD relative to BOD
• Presence of certain metal or nonmetal inorganic toxins
@ Individual flows from sources demonstrating a potential
for large pH fluctuations
• Limited amount of nitrogen and phosphorous compounds
relative to the potential carbonaceous biological
oxygen demand .
Process and cooling wastewaters from both petrochemical
and paper production plants arrive at the Washburn Facility with
a combined influent temperature between 35° and 41°C. During
175
-------
TABLE 68. NPDES EFFLUENT LIMITATIONS FOR THE
WASHBURN TUNNEL FACILITY (EFFECTIVE TO
kg/day (Ib/day) June 30, 1977
Parameter
Temperature C
pH
BOD
COD
TSS
O&G
Phenol
Sulf ide
Cyani de
Mercu ry
Total Cr
NH3-N
Fluoride
Zinc
Ti tani um
N03-N
TKN
TDS
Total P
Al umi num
Arsenic
Barium
Boron
Coba 1 t
Copper
Iron
Lead
Manganese
Mol ybdenum
Nickel
Selenium
Silver
Cadmium
Month
6,
68,
15,
2,
1,
7,
4,
505,
2,
1,
iy
—
736
714
382
230
871
49
15
84
668
389
56
997
843
735
170
302
868
28
712
117
68
35
163
33
141
39
39
4
2
2
Average Perm
. 5
.3
.497
. 5
.3
(1,1
.2
.8
.6
.3
.9
.9
. 34
.6
. 08
. 20
.49
(14,820) 1
(151 ,171 )13
(33,840) 3
(4,906)
(1,916)
(109)
(34)
(1.1)
(186)
(3,670)
(856)
(124)
(2,193)
(17,255) 1
(10,417)
11 ,374)1 ,01
(664)
(6,310)
(62.04)
(1 ,566)
(259)
(150)
(78.3)
(2,559.3)
(75)
(312)
(87)
(87)
(9)
(4.84)
(5.5)
i
3
7
0
4
1
3
1
5
9
0
1
5
1
2
t Li
46
9
,472
,400
,764
,460
,742
98
30
178
,337
777
112
,995
,686
,334
,339
,510
,736
56
,423
235
136
71
,326
67
283
78
79
8
4
4
mi t
°C
.0
. 9
.66
.493
. 0
. 5
.7
.31
.7
. 1
.7
.8
.8
. 7
. 2
. 156
.4
.971
(29,640)
(302,280)
(67,681)
(9,812)
(3,832)
(218)
(67.5)
(1 -09)
(392)
(7,341)
(1 ,711)
(248)
(4,389)
(34,509)
(20,534)
(2,222,746)
(3,322)
(12,619)
(123.9)
(3,131)
(519)
(299)
(156.4)
(5,118.7)
(149)
(624)
(173)
(174)
(18)
(9.7)
(10.9)
176
-------
TABLE 69.
REPORTED
Parameter
Zinc
Titanium
N03-N
TKN
TDS
Total P
Al umi num
Arsenic
Barium
Boron
Cobal t
Copper
Iron
Lead
Manganese
Mol ybdenum
Nickel
Sel enium
Silver
Cadmium
( Chromi urn)
(f-'ercury )
Zinc
Ti tani urn
N03-N
TKN
TDS
Total P
Aluminum
Arsenic
Bari urn
Boron
Cobal t
Copper
I ron
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Cadmi urn
WASHBURN TUNNEL FACILITY
MONTHLY MAXIMUMS 1976
(mg/t)
Average
0.46
14.3
4.0
16.8
1855 1
1 .2
15
<.003
.29
<1 . 0
.03
.15
5.02
.07
.77
<0.1
.09
< .01
< .01
< .01
0.35
0.002
kg/day (Ib/day)
78.4 (172.9)
2,446 (5,393) 1.
638 (1,407)
2,785 (6,141)
315,496(695,669) 186,
207 (456)
2,540 (5,601)
1.77 (3.90)
48.1 (106.1)
50.8 (112)
4.2 (9.3)
24.9 (54.9)
858 (1,892)
11.7 (25.8)
132 (291)
4.3 (9.5)
15.9 (35.1)
0.36 (0.8)
2.0 (4.4)
2.3 (5.1)
: AVERAGES OF
INFLUENTS
Range
.34 .65
7.0 23.7
<0.1 - 8.8
6.1 - 52.2
085 - 2435
0.26 2.25
6 29
0.1 1.1
.01 .04
.03 .26
4.18 6.80
.01 .15
.15 1 .05
.01 .18
.18 1.16
0.001- 0.005
53.5 111
108 3,837
16.3 2,566
987 8,921
710 384,639
42 89
995 4,817
<0. 163- ? . 16
16.3 174
26.2 89.4
1.36 6.8
12.7 44.5
510.7 1 ,101
<1 .63 39.0
24.5 193
3.27 4.98
1.63 32.7
<0.159- .816
<0.186- 3.6
<0.163- 5.4
177
-------
TABLE 70. REQUIRED LEVELS OF TREATMENT TO MEET 1976 NPDES
PERMIT EFFLUENT LIMITATIONS - WASHBURN TUNNEL FACILITY
Parameter
BOD
COD
TSS
O&G
Phenol
Sulfide
Cyanide
Mercury
Total Cr
NH3-N
Fluoride
Zinc
Titanium
N03-N
TKN
TDS
Total -P
Aluminum
Arsenic
Barium
Boron
Cobalt
Copper
Iron
Lead
Manganese
Molybdenum
Nickel
Selenium
Sil ver
Cadmium
NPDES Permit Limit-
Monthly Avg. (kg/day)
(effluent)
6,736
68,719
15,382
2,230
871
49.4
15.3
497
84.5
1,668
389
56.3
997
7,843
4,735
505,170
302
2,868
28.2
712
117.8
68
35.6
1,163.3
33.9
141.9
39.34
39.6
4.08
2.20
2.49 «
1976 Avg. Monthly
Loading (kg /day)
(influent)*
57,173
202,344
•119,077
5,315
663
203
24.5
<.204
27.4
1,329
253
78.4
2,446
638
2,786
315,496
208
2,540
1.77
48.1
50.8
4.17
24.9
858
11.7
132.4
4.31
15.9
3.08
1.95
2.27
%
Removal
Required
88
66
87
58
None
76
37
None
None
None
None
28
59
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
NPDES Permit Max.
Limit for any 1 day
(kg/day) (effluent)
13,472
137,439
30,764
4,460
1,742
98.9
30.7
0.993
178
3,337
778
113
1,995
15,686
9,334
1,010,340
1,511
5,736
56,31
1,423
235.7
136
71.1
2,326.7
67.8
283.80
78.68
79.2
8.16
4.41
4.97
1976 Reported Maximum
Loading (kg/day)
(influent)
152,887
457,172
348,618
27,495
4,077
3.142
103.4
0.830
186
17,380
735
111
3,841
2,566
8,921
389,639
361
4,817
2.16
174
84.4
6.8
44.5
1,101
39.0
193
4.98
32.7
.816
3.63
5.44
Approximate % Removal
Required/Comments
91
70
91
84
57
97
70
None
None
None
48
None
None
None
None
None
None
None
None
Nnnp
HUMt?
Nnnp
I1UI 1C
None
None
NnnA
If UIIC
None
None
None
None
8.6
Averages for parameters in bottom half of table are based on the reported maximums; derived from one sampling per month.
Averages for parameters in upper half are based on the reported monthly averages derived from multiple samples each month.
-------
the summer, the waste stream temperature may remain above 40°C
and may severely impact the biological population in the plant
bioreactor. Thermophi1ic bacteria may proliferate under such
conditions, but their instability and the occasional poor
settling characteristics of the resultant floe make their
presence undesirable. The time required for acclimation of
mixed biological cultures at high temperatures (above 40°C) has
been observed experimentally to be on the order of months (16).
A temperature control system must, therefore, be provided for
maintaining the wastes below this temperature if biological
treatment is to be applied effectively.
Oil and grease in wastewaters may be difficult to degrade
biologically in comparison with other carbonaceous materials.
Volatile organic constituents or metal-bearing compounds
associated with oils may also act as metabolic inhibitors or
destroy cell membranes. In higher concentrations, oil and
grease will form scums or slicks in treatment plant units. This
phenomenon can result in reduced oxygen transfer to the aqueous
waste and reduced surface area of the oily fraction for biologi-
cal attack. Spill ponds must, therefore, be provided for
diverting high TOC wastes suspected of being rich in oil and
grease. The hydrophobic nature of oil and grease means that
continuous dispersion forces must be present in the bioreactor
if these materials are to be adequately degraded.
Research has shown that biological treatment of phenolic
wastewaters has been successful at concentrations under 500 mg/l
(137). Biological techniques have reduced phenol concentrations
in wastewaters at 150 to 250 mg/l by 97 percent. Below a
150 mg/l concentration, biological removal is often complete.
It must be noted, however, that biological treatment plants are
vulnerable to sudden increases in phenol loading rate. Influent
wastes at the Washburn Tunnel Facility demonstrated a maximum
phenol concentration of 24.8 mg/l during 1976. This concentra-
tion is well below the threshold concentrations for successful
biological treatment.
The organic content of the Washburn Tunnel Facility influent
is low when compared with typical organic chemical waste streams.
The following 1976 averages were calculated:
Average level in influent
Parameter during 1976 (mg/l)
BODs 338
COD 1,199
TOC 184
179
-------
COD concentration is approximately 3.5 times that of BOD and
is indicative of the fraction of dichromateoxidizable materials
amenable to biological degradation (46). The ratio for the
Washburn Tunnel Facility indicates that a substantial portion
of the organic wastes is not readily amenable. The ratio for
other chemical industry wastes is usually around 3.0 to 6.0.
It would appear from the high ratio of COD- to TOC that a
portion of the COD is attributable to inorganic oxidation.
Sulfides, sulfites, thiosulfates, nitrates, or ferrous iron
may also be responsible for some of the COD reported in the
influent.
The stability of organic carbon and oxygen demand parameters
is often taken to be an indicator of the amenability of waste to
biological treatment. Figures 28 and 29 show the variations in
the concentrations and loadings of these parameters in the
influent wastes during 1976. The range of reported monthly
averages and the lowest and highest reported monthly maximum for
any one sample are as follows:
Range of the
monthly
Parameter
BOD5
COD
TOC
avera
265
1 ,040
165
ges (mg/£)
-453
-1 ,306
-219
Lowest reported
month!y
minimum (mg/£)
147
577
64
Highest reported
monthly
maximum (mg/l)
854
2,717
430
Reported monthly maximums are relatively low compared to
typical organic industrial wastes and cannot be considered
"shock" loadings. The large fluctuations in COD shown in
Figures 28 and 29 are probably due to the highly variable
organic nature of one or more of the contributing waste streams.
This can be caused by intermittent discharges from batch process
areas and points out the need for spill ponds and equalization
facilities.
The complex nature of industrial wastes or
estimate of metal toxicity difficult. Toxicity
in terms of the method of biological treatment,
ment for metal removal, the nature of microbial
the bioreactor, and operational parameters such
ing and sludge age. Raw waste flows may contai
compounds which can form complexes with metals
toxicity. Waste streams may also contain other
may have synergistic or antagonistic effects wi
Unless the types of reactive organic and inorga
in the wastes are known, it is difficult to gai
the toxic behavior of specific metals (124).
sewage makes an
must be defined
any pgetreat-
populations in
as rate of mix-
n chemical
and reduce their
cations that
th heavy metals.
nic constituents
n insight into
180
-------
1400
1300 -
1200
1100 -
1000 -
900 -
800 -
mg/£
600 -
500 -
400 -
300 -
200
100 -
I
F
1199 YEARLY AVG
COD
A
BOD
338 YEARLY AVG
TOG
184 YEARLY AVG,
M
I I I I
M J J A
MONTH (1976)
i
S
N
Figure 28.
Washburn Tunnel Facility influent concentrations (ppm)
monthly influent/effluent reports - 1976.
181
-------
250
COD AVG.= 202.3
200
150
o
o
o
100
O
BOD
50
TOC
I
F
!
M
I
M
AVG,- 57,2
AVG,= 31,3
I
J
I
A
r
o
i
N
MONTH (1976)
Fi gure 29.
Influent to Washburn Tunnel treatment plant
(Avg. 1976 flow= 169,9 x 103m3/day)
182
-------
The average of the reported monthly maximum heavy metal
concentrations in the influent waste is included in Table 69.
The maximum level of chromium was 1.16 mg/£. Studies of the
impact of chromium upon activated sludge systems show that a
concentration of 50 mg/£ is required to affect BOD removal
efficiency (73). Copper is also present in innocuous concentra-
tions (1976 maximum = 0.26 mg/£). It would probably require a
dose an order of magnitude more concentrated before biological
treatment efficiencies were impaired. Studies on the effect of
zinc on the efficiency of biological processes in removing
organic matter showed that up to 10 mg/£ zinc in plant influent
has no discernable correlation with COD or BOD levels in the
final effluent (73). The maximum zinc concentration reported
at the Washburn Tunnel Facility in 1976 was 0.65 mg/£. Nickel
is also present in the waste in concentrations well below those
that have been shown to be deleterious to activated sludge plant
efficiency.
Nonmetal materials present in the influent waste in trace
quantities are arsenic, boron, selenium, cyanide, and various
organic and inorganic sulfide compounds. Of these, arsenic,
cyanide, and the sulfides can be inhibitory to microbiological
degradation of organic substrates. A summary of the concentra-
tions of these constituents in the Washburn Tunnel Facility
waste influent follows:
Avg. of reported Highest reported
monthly maximums 1976 monthly maximum
Constituent
Arsenic
Cyan i de
Sul f i des
(1976)* (mg/£)
<.003
0.32
4.. 81
in ( m g / 1 )
0.57
18.24
*Arsenic: 1 sample per month
Cyanide and sulfides: 13 samples per month.
Arsenic is a recognized biocide and may be converted to
highly toxic methyl derivatives by bacteria. However, at a
concentration of less than 3 u g / £, it is doubtful whether the
traces of arsenic in the Washburn Tunnel Facility influent have
any inhibitory effect upon either biological processes at the
plant or the receiving environment.
The average of the monthly maximums for cyanide in 1976
indicate that this compound is present in "borderline" concentra
tions where inhibition of biodegradation is questionable. In
quantities above 0.5 mg/£, cyanide may appreciably inhibit both
183
-------
nitrification and microbial respiration. Moreover, activated
sludge has shown a capability to metabolize cyanide. Cyanide
present in the concentrations detected in the Washburn Tunnel
Facility should not be a problem to biological processes, if
the bioreactor is completely mixed and receives sufficient
aeration. The reported sulfide levels may also be reduced by
oxidative processes in the treatment scheme.
Although the pH of individual waste sources, as shown in
Table 64, ranged between 1.8 and 11.1, in 1976 the yearly
average for the combined flow was 8.0. The waste pH is stabi-
lized because the largest waste source (76 percent of the total
flow) has an average pH of 8.2. The remaining industrial flows
tend to neutralize one another upon mixing. However, under
certain conditions, it is possible that the wastes could become
overly acidic or alkaline, depending upon in-house plant
operations and periodic increases in the flows of certain
contributing waste streams. A capability for neutralization of
the mixed waste prior to introduction to the bioreactor should,
therefore, be provided.
Nutrient adjustment can be accomplished by adding
phosphoric acid as required. Nitrogenous compound levels in
Influent B should contribute a substantial amount of the nitro-
gen required for biological metabolism. It is apparent that
some additional nutrients, particularly phosphorus, may have to
be added to provide an acceptable carbon/nitrogen/phosphorus
rati o.
TREATMENT SYSTEM CONSTRUCTION AND DESIGN
Overal1 System
In constructing the Washburn Tunnel Facility, circular and
rectangular sedimentation and aeration basins were excavated
and cast. There are 25 aerators (with a total horsepower
of 3,390) in the aeration basins; sludge collection equip-
ment is installed in the various clarifiers. Additional
equipment includes waste and sludge transfer piping, neutraliza-
tion facilities, a cooling tower, and sludge handling facilities.
The facility also has advanced monitoring equipment and a
centralized control station. During 1976, the GCWDA *i nstal 1 ed
a large fluidized bed incinerator.
Figure 30 shows the process flows through the plant.
Influents A, B, C, D, and F enter the treatment system through
bar screens where large debris is removed. A total flow of
approximately 1.7 x 10b m3/day (45 MGD) con tai ni ng about 55,000
kg (121,254 Ib) of BOD is treated each day. The wastes then pass
through a grit removal chamber where sand, grit, and other
abrasive material settle.
184
-------
HOUSTON SHIP CHANNEL
03
cn
Ba. FINAL CLARIFIERS (OLD)
Bb. FINAL CLAHIFIERS (NEW)
9. FILTER PRESS BLDG.
10. INCINERATOH
11 BARGt
1. BAM SCREEN
2. CHIT CHAMBER
3. PRIMARV CLARIFIER
4. NEUTRALIZATION
S. NUTRIENT ADDITION
6. COOLING TOWER
la. AERATION BASIN (OLD) 12. HOLDING DASINS
7b. AERATION BASIN (NEW) 13 LAD & OFFICE BLDG.
INFLUENTS
A, B. C. D, AND
Figure 30. Process flows through'the GCWDA Washburn Tunnel facility.
-------
Two 64-meter diameter primary clarifiers (T-10 and T-ll)
are used to remove suspended solids that settle during the 3-hr
retention. A total of 2,722 t (3,000 tons) of primary and
biological sludge (1 to 2 percent solids) is removed from the
clarifiers each day and wasted to the sludge processing/disposal
facilities. The clarified waste then flows to a neutralization
basin where sulfuric acid may be added to lower waste alkalinity.
Phosphoric acid is added as a nutrient source when necessary; the
nitrogen nutrient requirement is provided by ammonia.
A cooling tower is used to cool the waste to about 40°C in
the summer. Figure 31 shows views of the cooling tower. A
portion of the warm influent may be pumped to the top of the tower
and cascaded down onto the redwood impingers. When cooling is
not needed, wastewater flows directly to the aeration basins
where the waste is completely mixed by surface aerators with
sludge recycled from the secondary clarifiers. Figure 30 shows
how the waste flow from the equalization basin/cooling tower area
is split into two separate flows and channeled to aeration basins
T-19, T-20, or T-21. From this point on, there are two parallel
but dissimilar secondary biological systems. Lime is occasional-
ly added to the aeration basins for pH adjustment.
From the aeration basins, the biologically treated wastewater
flows to the secondary clarifiers. Two 61-m-diameter
clarifiers (T-16 and T-17) receive waste flows from aeration
basins T-19 and T-21; the four smaller clarifiers (27A through D)
receive wastes from aeration basin T-21. Part of the settled
solids from the secondary clarifiers is pumped back to the
aeration basins, and part is pumped along with sludge from the
primary clarifiers to removal, dewatering, and disposal facili-
ties. The biologically treated and clarified effluent then
overflows the clarifier weirs and discharges to the Houston Ship
Channel .
System specifications for the Washburn Tunnel Facility are
shown in Table 71. Approximately 1.33 x 105m3/day (3.5 MGD), or
78 percent of the total flow, passes through the primary
clarifiers before entering the equalization basin; it is then
mixed with the remaining 22 percent of the total flow (Influent
E). The flow is then split to the two aeration basins; about
1.17 x 10bm3/day (3.1 MGD) (69 percent) goes to basins*T 19 and
T-20 and 5.32 x 104m3/day (1.4 MGD) (31 percent) goes to basin
T-21. However, these are only estimates, as the relative flows
to one basin or the other can be altered.
OPERATIONAL INFORMATION
Data describing the Washburn Tunnel Facility system opera-
tions and internal waste stream characteristics came from two
sources :
186
-------
"71
ro r- zi •
r-zo
Figure 31.
Washburn Tunnel facility
cooling tower.
187
-------
TABLE 71. UNIT CAPACITIES: WASHBURN TUNNEL FACILITY
Co
Co
Unit
Primary clarifiers
T-10, T-ll
Aeration Basins
(old) T-19, T-20
Aeration Basins
(new) T-21
Final Clarifiers
(old) T-16, T-17
Final Clarifiers
(new) 27A-D
No. of
Units Width Diameter
64 m
2 — (210 ft)
48.8 m
2 (160 ft)
56.1 m
1 (184 ft)
60.96 m
2 -- (200 ft)
30-48 m
4 (100 ft)
Length
--
76.2 m
(250 ft)
64 m
(210 ft)
--
30.48 m
(100 ft)
Depth
4.57 m
(15 ft)
4.88 m
(16 ft)
4.57 m
(15 ft)
3.66 m
(12 ft)
5.18 m
(17 ft)
Approx.
Flow Retention
Volume (m3/d Time
15.5 ML
(4.1 MG) 132.5 x 1C3
18.09 ML
(4.78 MG) 58.7 x 103
17.0 ML
(4.5 MG ) 53.2 x 103
10.7 ML
(2.82 MG) 58.7 x 103
5.0 ML
(1.32 MG) 13.3 x 103
2.8 hr
7.4 hr
7.7 hr
4.4 hr
9.1 hr
-------
• Chemical usage records
t Monitoring at specified stations.
Information on the percent of total flow diverted to the various
aeration basins, percent sludge wasted, feed rates to the sludge
centrifuges, and other important operational specifications were
also available.
Monthly chemical usage data are summarized as the average
daily consumption for 1976:
Chemi ca1
• Primary polymer
• Su1furi c acid
• Phosphoric acid
• Liquid ammonia
• Diatomaceous earth
• Lime
Average daily
consumption (1976)
2,837 kg/day (6,255 Ib/day)
1.43 m3/day
5.61 m3/day
0.70 m3/day
3,906 kg/day (8,621 Ib/day)
2,555 kg/day (5,634 Ib/day)
The sulfuric acid and lime are used for pH control and sludge
conditioning. The addition of concentrated phosphoric acid and
liquid ammonia at the rates specified above is equivalent to a
nitrogen loading rate of 336 kg/day (740 Ib/day) as nitrogen
and a phosphorus loading rate of 2,948 kg/day (6,500 Ib/day) as
phosphorus .
Sampling station locations for monitoring internal waste
stream characteristics are shown in Figure 32. Temperature,
pH, Imhoff settleability, total organic carbon, and suspended
solids are measured at the "primary effluent" station, T-31.
Sampling is conducted where the clarified aqueous effluents
from basins T-10 and T-ll combine. The second internal sampling
station for waste stream flow is at the influent to the aeration
basins (station AI). Here, only pH and temperature are
monitored. Samples taken from stations in aeration basins T-19,
T-20, and T-21 are measured for dissolved oxygen, dissolved
oxygen uptake (mg of oxygen demand exerted in one hour), mixed
liquor and volatile suspended solids, and the sludge volume
index.
Average 1976 monthly values for the primary effluent
station (T-31) and the aerator influent station (AI) are shown
in Table 72. Raw waste influent data for 1976 indicated a pH
of 8.0, a TOC of 184 mg/f, and suspended solids of 704 mg/£.
The data in Table 72 indicates a neutralization of the pH and
63 and 72 percent reductions in TOC and TSS loading respectively
189
-------
GCWDA SAMPLING STATIONS
I = INFLUENT
PE = PRIMARY EFFLUENT (T-31)
AI = AERATOR INFLUENT
T-19, 1-20, 1-21 = AERATION BASINS
HOUSTON SHIP CHANNEL
OUTFALL
COOLING
TOWER
FLOW \^
INFLUENT E
1 DAM SCREEN
2. GRIT CHAMBER
3. PRIMARY CLARIFIER
4. NEUTRALIZATION
5. NUTRIENT ADDITION
6. COOLING TOWER
7a. AERATION BASIN (OLD)
7b. AERATION BASIN (NEW)
8s. FINAL CLARIFIERS (OLD)
• Bb. FINAL CLARIFIcRS (NEW)
9. FILTER PRESS BLDG.
10. INCINERATOR
11. BARGE
12. HOLDING BASINS
13. LAB 6 OFFICE BLDG.
INFLUENTS
A, B, C, D, AND F'
Figure 32. Washburn Tunnel Facility: GCWDA existing sampling stations.
-------
TABLE 72. 1976 DATA FOR PRIMARY EFFLUENT AND AERATOR INFLUENT
Primary effluent (station T-31)
Imhoff TOC TOC Suspended solids Suspended Solids
pH Temp. °C ml/I (mg/l) kg/day (Ib/dav) (mg/l) kg/day (Ib/day)
7.1 36.8° 1.7 176.6 11,449 (25,245) 194 32,673 (72,044)
Aerator Influent (station Alj
pH Temp. °C
7.1 36.7°
-------
Data for Station AI indicate that the pH and temperature of the
waste as it enters the aeration basins are similar to those of
the waste leaving the primary settling basins. Although the
average temperature of the aeration basin influent in 1976 was
36.7°C (98.1°F), the lowest monthly average was in December
31.1°C (88.0°F), while the highest was in August and was 40°C
(104°F). The waste temperature appears to be directly related to
the ambient air temperature. During the summer, the cooling
tower must be used to maintain the influent and aeration basin
temperatures at or below 40°C (104°F). Otherwise, undesirable
thermophi11ic microorganisms will be favored in the basins.
Average monthly values at the three aeration basins in
1976 were as fol1ows:
Basin
T-19
T-20
T-21
(
3
4
3
DO
mg/£)
.95
.03
.68
DO
(mg
32.
28.
32.
uptake
/*)
75
75
83
2
2
3
MLSS
(mg/£)
,433.33
,541.67
,291.67
MLVSS
1,603.
1,640.
2,107.
25
33
08
S
9.
8.
8.
VI
53
65
89
14,217 kg/day (31,341.75 Ibs/day)
12,480 kg/day (27,513.75 Ibs/day)
13,388 kg/day (29.514.17 Ibs/day)
0.4
0.4
0.3
1 .6
1 .5
1 .1
1.1
1 .1
1 .5
The total oxygen demand based upon the stated volumes of the
various aeration basins was calculated as were the F/M ratio,
as kg influent BOD/kg MLSS and as kn influent COD/kg MLSS.
Sludge age was determined from (mg/.£ MLSS) x (basin volume) x
(million liters) x (mg/£ influent SS)/(flow to basin (ML/DAY).
The results were as follows:
F/M ratio
Total oxygen demand F/M ratio (kg COD/kg Sludge
Basin (TOD) from DO uptake (kg BOD/kg MLSS) MLSS) age (days)
T-19
T-20
T-21
The calculated F/M ratios are actually somewhat low because of
the removal of an unquantified amount of BOD and COD in primary
clarification. Nevertheless, the calculated ratio corresponds
to a high rate, completely mixed activated sludge system treat-
ing industrial wastes. The F/M ratio is calculated on a daily
basis to determine necessary adjustments in the rate of sludge
return.
An average feed rate to the centrifuges of 142 m3/day was
maintained during 1976. This flow is approximately 9.1 percent
192
-------
solids. Sludge wasted from the primary clarifiers is 1 to 2
percent solids.
TREATMENT EFFICIENCY
Tables 73 and 74 show the average 1976 concentrations and
loadings, respectively, for constituents in the Washburn Tunnel
Facility effluent. These data are filed monthly as part of the
influent/effluent report in compliance with the NPDES discharge
permit requirements. The effluent quality should be compared
with the influent quality (Tables 66 and 69) to determine overall
treatment efficiency. Table 75 shows the results of this com-
parison in terms of kilograms of constituent removed per day and
percent of efficiency-
The graphs in Figures 33 and 34 show the fluctuations of the
concentrations and loadings of organic constituents, expressed
as TOC, 8005, and COD during 1976. Comparison with similar
graphs for plant influents (Figures 28 and 29) indicates that
all three waste parameters are significantly reduced. The range
of reported monthly averages and the lowest and highest reported
monthly maximum for any one effluent sample are given below.
Lowest reported Highest reported
Range of the monthly monthly minimum monthly maximum
Parameter averages (mg/l) (mg/l) (mg/l)
BOD5
COD
TOC
13 - 35
254 - 388
103 - 144
6
200
54
76
760
313
The average reductions in BOD5, COD, and TOC for 1976 were 93,
72, and 36 percent, respectively. These efficiencies indicate
that a large portion of inert organic material is passing
through the system. It is unlikely that this material is
phenols or oil and grease, since these constituents are reduced
98 and 88 percent, respectively. Furthermore, the organic
materials in the effluent are not readily biodegradable. For
example, most (93 percent) of the raw influent BODc is satisfied
by the treatment process. There are not sufficient data to
provide detailed descriptions of specific discharge organic
compounds; further investigations are needed to determine their
identity and concentrations.
Comparisons of month-to-month fluctuations in both influent
and effluent organic constituents show that the long retention
time and complete-mix bioreactor tend to reduce influent
fluctuations and provide an effluent of predictable quality.
Detailed raw waste characterization, nutrient addition,
193
-------
TABLE 73. WASHBURN TUNNEL FACILITY - 1976
EFFLUENT QUALITY SUMMARY
Parameter (mg/£)
BOD 22.9
COD 331.8
TSS 50.7
Oil and grease 3.6
Phenol 0.06
Sulfide 0.11
Cyanide
Mercury
TOC 117.2
Total Cr 0.06
Color 594.0
NH3-N 4.4
Fluori de 1.4
Zinc 0.2
Titanium 2.4
N03-N 0.8
TKN 9.3
TDS 1856.3
Total P 0.64
Aluminum 2.0
Arsenic
Barium 0.17
Boron
Cobalt 0.02
Copper 0.04
Iron 1.07
Lead 0.03
Manganese 0.51
Molybdenum
Nickel 0.05
Selenium
Silver
Cadmium
194
-------
TABLE 74. WASHBURN TUNNEL FACILITY - 1976
EFFLUENT QUALITY SUMMARY
Parameter Average kg/day (Ib/day)
BOD 3,868 (85,289)
COD 55,922 (12,308)
TSS 8,582 (18,923)
Oil and grease 620 (1,367
Phenol 10.1 (22.3)
Sulfide 15.fi (34.4)
Cyanide
Mercury
TOD 19,909.7 (43,901)
Total chromium 10.0 (22.1)
Color 100,757.0 (222,169)
NH3-N 736 (1,623)
Fluoride 235 (518)
Zinc 38.7 (85.3)
Titanium 409.9 (904)
NOs-N 134 (295.5)
TKN 1,546.9 (3,411)
TDS 312,463.4 (688,982)
Total P 108 (238)
Aluminum 336.4 (741.8)
Arsenic
Barium 28.5 (62.8)
Boron
Cobalt 2.9 (6.4)
Copper 8.8 (19.4)
Iron 184.0 (405.7)
Lead 5.2 (11.5)
Manganese 88.0 (194)
Molybdenum
Nickel 8.8 (19.4)
Selenium
Silver
Cadmium
195
-------
TABLE 75. WASHBURN TUNNEL FACILITY: 1976 OVERALL TREATMENT PLANT
EFFICIENCY
Percent, efficiency
Average kg/day (Ib/day removed (influent-effluent/influent)
Parameter
BOD
COD
TSS
Oil and
Phenol
Sulfide
Cyanide
Mercury
TOC
Chromium
Color
NH3-N
Fluoride
Zinc
Titanium
NO.-N
TKN
TDS
Total P
Aluminum
Arsenic
Barium
Boron
Cobalt
Copper
Iron
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Cadmium
grease
53,298
146,404
110,481
4,695
652.1
187.6
- 22.9
> 0.04
11,343
17.3
-19,052
593
18
39.6
2,036.1
5.° 3
1,236.5
3,035.1
99
2,203.0
19.6
1.7
848.8
673.6
6.4
44.5
(117,522)
(322,821)
(243,611)
(10,352)
(1,437.9)
(413.7)
(>50.5
(0.09)
(25,011)
(38.1)
(1 ,307.6)
(40)
(87.3)
(4,489.6)
(1,108)
(2,726.5)
(6,692.3)
(218)
(4,857.6)
(43.2)
(2.9)
(1,872)
(1,485)
(14.1)
(98.1)
7.1 (15.7)
93
72
93
88
98
92
94
20
36
63
(increase)
45
7
51
83
79
44
1
48
87
41
32
99
79
55
34
45
196
-------
1400.
1300-
1200.
1100.
1000 .
900 -
800 -
700 -
600 _
500 -
400 -
300 _
200 -
100 -
COD
BOD
AVG,= 22,9
M J J A
MONTH (1976)
0
N
Figure 33.
Washburn Tunnel Facility effluent concentrations (ppm)
monthly influent/effluent reports - 1976.
197
-------
250
200
o
o
o
150
Q
\
O
100
AVG.= 56.0
50
TOC
BOD
•»
AVG.= 3.9
M
-i -T r——r-
M J J A
MONTH (1976)
O
T"
N
D
Figure 34.
Effluent from Washburn Tunnel treatment plant
(avg. 1976 flow = 169.9 x lQ3m3/day).
198
-------
controlled sludge wasting, and high-volume, complete-mix
bioreactors with influent temperature control all account for the
high BOD removal by the Washburn Tunnel plant.
By evaluating the data describing nitrogen and phosphorus
species in the plant influents, chemical additions, and plant
effluents, a mass balance for nutrients may be estimated and
compared with the amount of carbonaceous material being bio-
logically oxidized in the aerobic treatment process. While
such an analysis does not consider the fact that certain types
of microbes in the treatment plant may not be able to utilize
certain forms of nutrients, e.g., ammonia nitrogen, and nitrogen
and phosphorus bound in complex organic molecules, it does
indicate the nutrient dynamics of a biological system success-
fully treating BOD in a complex industrial work.
The majority of the complex organic nitrogen, nitrate
nitrogen, and total phosphorus in the process influent originates
from the kraft paper mill. Nitrogen, as ammonia, originates
from all of the waste contributors. Figure 35 shows the average
1976 loadings for each of the nutrient species from industries
and chemical additions at the plant, as wel.l as the loading of
biologically degradable carbon. The latter was calculated from
BOD loading values by assuming that one mole of oxygen combines
with one mole of carbon in aerobic respiration to yield carbon
dioxide. As indicated in Figure 35, several important variables
necessary for completely characterizing the plant's nutrient
balance are presently unquantified. Nutrient removal from the
system via primary and secondary sludge wasting is not included.
Based upon known influent/effluent quantities, the BOD:N:P
ratio of the biooxidation in the aeration basins is approximate-
ly 100:9.8:1.6. However, significant removal of phosphorus may
be occurring by sorption to sludge in the secondary settling
process. This would reduce the estimate for phosphorus, bring-
ing the overall ratio more in line with the 100:10:1 estimate for
aerobic bioconversion. Presently, nutrients are added so that
trace amounts are continuously detected in the aqueous effluent.
Reduction in costs for chemical addition may be achieved by
monitoring nutrients in the secondary sludge or adding an
influent waste stream rich in phosphorus.
ECONOMIC EVALUATION
The primary settling facilities at the GCWDA Washburn
Tunnel Facility were originally constructed by Discharger 1 in
1967. In 1971, a cooling tower, the two older aeration basins
(T-19 and T-20), secondary settling basins T-16 and T-17, and
sludge centrifuges were added. In May 1973, contracts between
the GCWDA and the waste-generating industries were signed and
the state called for the sale of $25 million in bonds, of which
$12.5 million went to purchase the existing plant. Under agreed
terms, the industries are paying all bond amortization, plant
199
-------
ARCD-200
1NFLUENT
TOTAL N = 277 PS/DY
TOTAL P = O.OKG/DY
BDC* c 0.32 KG/DY
PRIMARY
INFLUENT
ro
O
O
TOTAL N = 3638 KG/DY
TOTAL P = L52 KG/DY
BDC* = L9686 KG/DY
CHEMICAL
ADDITION
TOTAL N = 336 KG/DY
TOTAL P = 2948 KG/DY
ODC* = O.OKG/OY
AERATION BASINS
19666 + 0.32 - 1451 ? 16235 KG/DY
3838 + 277 -f 336 - 1661 = 2770 KG/DY
152 + 2948 - 106 = 2992
CiNiP = 100il5il6
(IDEAL CtNlP = lOOilOil)
EFFLUENT
RETURN SLUDGE
TOTAL N = UNKNOWN
TOTAL P = UNKNOWN
BDC* = UNKNOWN
WASTE SLUDGES
TOTAL N = 1681 KG^DY
TOTAL P = 108 KG/DY
TOTAL BDC* = 1451 KG/DY
*BDC •• BIOLOGICALLY DEGRA%ABLE CARBON.
CALCULATED AS B*OD5 X 0.375
TOTAL N - UNKNOWN
TOTAL P •= UNKNOWN
BDC* = UNKNOWN
Figure 35. Washburn Tunnel Facility: approximation of nutrient balance
-------
maintenance, and operating costs, plus a management fee to the
GCWDA of $120,000 annually.
In 1976, an expansion program was begun which provided the
additional biological train (aeration basin T-21) and four
secondary settling basins (T-27A, B, C, and D), and sludge hand-
ling facilities (filter presses), expanding the plant capacity
to approximately 208 million £/d. The total cost of this
expansion was $14 million and was financed by the remainder of
the original bond issue. The total construction for the entire
facility is estimated to be $26 million. A construction
cost summary is shown in Table 76. Costs were derived from
survey estimates and updating and scaling of estimates for an
activated sludge system treating industrial wastewater in the
Gulf Coast region as developed by Hovious (66). Specific engi-
neering cost indices were used for updating to 1976 dollars.
Estimates for the Washburn Tunnel Plant, where taken from the
Hovious data for a 3.8 x 10^ m^/day (1.0 MGD) system, were
obtained by multiplying the cited cost data by 4.5. The
estimated 1976 operation and maintenance costs for the facility
are shown in Table 77. The total cost was $4,332,700. Mainte-
nance costs which were estimated as two percent of total
construction cost represent 23 percent of the total operation
and maintenance cost. This portion is in agreement with present
estimates of between 20 and 25 percent by GCWDA plant officials.
Operation labor and supervision was based upon a plant staff
of 5 supervisors and 34 laborers. Data on daily chemical usage
were used in conjunction with supplier estimates for bulk
chemical costs to derive an estimate for the 1976 chemical costs
at the facility. Power costs were based upon a ratio of known
costs at the GCWDA 40-Acre Facility in Texas City to that
facility's total aerator horsepower. Additional miscellaneous
power for pumping and sludge raking and processing is not
included. The sludge disposal costs are estimated using a unit
processing cost per kilogram of BOD removed derived from cost
discussions by Hovious (66). The estimate is updated to 1976
do!1ars.
201
-------
TABLE 76, WASHBURN TUNNEL FACILITY:
ESTIMATED CONSTRUCTION COST SUMMARY*
Neutral ization
Structural
Mixing
Reagent storage
pH' control
Primary clarification
Structural
Mechanical equipment
Equalization
Structural
Concrete liner
Mixing
Aerobic has in
Earthwork and roadway
Concrete liner
Aeration equipment
Aeration equipment support
Electrical support
Final clarification
Structural
Mechanical equipment
Piping
Instrumental on
Building and lab equipment
Site preparation
Land at $5,000/acre x 24 acres
Sub-total
Construction contingency
Construction cost
$ 270,500
114,300
373,700
147,500
1 ,519,400
725,300
960,100
213,900
245,900
31 1 ,000
1 ,106,400
6,195,700
3,442,080
823,600
2,641 ,800
1 ,376,800
1 ,397,300
614,700
688,400
347,900
120,100
23,636,^00
2,363,600
$ 26,000,000
Determined from cost estimates for a 37.9 x 10 l./d activated
sludge plant treating industrial wastes in the Gulf Coast area
1971 costs were upgraded to 1976 costs using Engineering News
Record indexes. Costs were then adjusted according to plant
size and known total construction cost.
202
-------
TABLE 77. WASHBURN TUNNEL FACILITY:
ESTIMATED O&M COSTS - 1976
Operating labor and supervision $ 480,000
t 5 Supervisors
t 34 Laborers
Chemicals 310,000
Power 260,000
(Aeration HP x 77.78)*
Maintenance
(2 percent of construction) 520,000
Misc. supplies** 6,700
Sludge disposal** 486,000
(BODr x $0.034/kg BODr x
10 percent annual inflation
since 1971 )
Amortize investment*** 2,270,000
(20 Years at 6 percent)
Total $ 4,332,700
cost/kg BOD removed = $0.223/kg
cost/kg COD removed = $0.081/kg
From aeration and power cost data at 40-Acre Facility.
From 1971 data presented in reference $"7 .
Capital recovery factor = 0.08718. Salvage value not included
***
203
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ICI DEEP SHAFT AERATION PROCESS
PARIS, ONTARIO, CANADA
INTRODUCTION
Eco Research Ltd., a wholly-owned subsidiary of Canadian
Industries Limited (CIL), has installed an experimental ICI Deep
Shaft pilot treatment facility in Paris, Ontario, Canada. This
relatively small innovative facility is operated by Eco Research
Ltd. and treats a portion of the industria1/domestic blend of
wastewater received at an extended aeration sewage treatment
plant. The Eco facility is located adjacent to the final
clarifier of an extended aeration plant operated by the Ministry
of Environment of the Province of Ontario. Industria 1/municipal
influent into the STP is separated by a splitter box and a
portion sent to the Deep Shaft plant. This facility is capable
of treating 4.7 x 102 nWday (0.2 MGD) of difficult-to-treat
industrial/domestic blends, with a total retention time of 30
min. The industrial waste components are received from 14
sources; the major contribution is a textile plant.
The Deep Shaft Process is a secondary biological process
utilizing a totally enclosed subsurface aeration shaft. Fluid
pressure increased with depth creates increased oxygen solubility
and enhances the oxygen transfer efficiency.
HISTORY
The original research and development work for the ICI
Deep Shaft Process was carried out in Britain by Imperial Chemical
Industries Ltd. (ICI), the parent company of CIL. In early 1974,
ICI constructed a prototype Deep Shaft Plant at the site of an
existing municipal sewage treatment plant at Billingham in the
northeast of England. This plant treated a small portion of the
flow to the main sewage treatment plant. The effluent from the
prototype was returned to the main plant. Experimentation con-
tinued until April 1975, when the Deep Shaft Process was made
commercially available. The first plant was sold to an industrial
client, Emsland Starke of Emlichheim, West Germany.
The plant at Emlichheim has been operational since October
1975. It is an industrial pretreatment facility that reduces
the strength of potato waste prior to discharge to a lagoon
system.
Another Deep Shaft demonstration facility is in operation
at Molson's Brewery in Barrie, Ontario, Canada. This plant is
204
-------
designed to treat approximately 3.4 x 102 m3/.day (0.9 MGD) of
brewery waste and has been operating successfully since mid-
February 1977.
The treatment facility at Paris, Ontario, was designed and
constructed in 1976 by Eco Research Ltd. as a research and
development facility. The facility treats a portion of the
industrial/domestic blend of wastewater received at the Paris
sewage treatment plant operated by the Ontario Ministry of the
Environment. Eco Research Ltd. has developed an alternative
approach to the separation of solids from that used by its parent
company in Europe. The process as developed by ICI utilizes
conventional gravity clarification following the Deep Shaft Process
However, because of extremely high dissolved gas content in the
effluent passing from the shaft, degassing equipment is required
between the clarifier and the shaft. The alternative approach
developed by Eco Research Ltd. which proved to be more cost
effective uses a flotation unit to remove the solids from the
effluent leaving the Deep Shaft.
The Paris facility has been in existence since July 1976
and has performed considerable R&D work related to solids separa-
tion. Because this work was time-consuming and because of the
high industrial component in the influent, the Deep Shaft Process
did not achieve optimization until March 1977. The demonstration
facility then operated on a continuous basis for six months, from
March to July 1977. Additional research will be performed at
the facil ity in 1978.
Location
The Eco Research facility is located in a residential area in
Ontario (Figure 36). The site is on the east bank of the Grand
River, which is the receiving water for the MOE extended aeration
discharge- Paris (population 7,500) is located approximately
60 km southwest of Toronto, Ontario. Figure 37 is a local map
of the Paris area.
Regional Characteristics
The physical surroundings of the Paris ICI facility consist
of relatively flat, rolling farmlands. The annual total precipi-
tation is in excess of 102 cm/yr, and the temperature ranges from
subzero during winter months to low and mid thirties (degrees
centigrade) during summer months. The completely enclosed
facility is minimally affected by abiotic factors of temperature
change and rai nfal1.
WASTEWATER IDENTIFICATION
For a number of reasons wastewater chemical characterization
for the Paris facility is presently limited. Since there has not
205
-------
ro
o
en
TORONTO
Osprmgc^/7 " ^ Cotta
•@/?i7 New|Hamburg
Beamwiller^land^J 17
Qnondaga / ABinbroofc
Caisto7VSmithvill!
B15\ _ j^h^/^WMd^ekA^^^X^01^
ns Colborne Crystal |
ach
BelmontV vllle t \ Rmwm
Figure 36. Paris, Ontario regional map.
-------
The Town of
PARIS
O SCO I20C 1900 2-WO 3COO
Figure 37. Paris, Ontario local map
207
-------
been regular monitoring for specific organic constituents, exact
chemical constituents of influent streams from each contributing
industry have not been analyzed. This makes it impossible to
compile comprehensive influent summaries. Also, the plant has
only been operating in the present mode for several months, so a
limited amount of waste data is available. Nevertheless, the
limited waste characterization data can be qualitatively augmen-
ted by identifying the types of on-line industries and the kinds
of process wastes issuing from each industry. The general process
waste categories from the 14 industrial contributors are: textile,
(approximately 60 percent of the total industrial flow), pharma-
ceutical, food processing, petrochemical, and printing. The typi-
cal wastes associated with the contributing industries are numer-
ous and comprised of many organic and inorganic chemical consti-
tuents. An exhaustive literature review resulted in an exten-
sive list of general categories and quantities of organic wastes
that might originate from each industrial contributor. Repre-
sentative compounds, listed below, were chosen on the basis of
solubility, polarity, and amenability to gas/liquid chromatogra-
phy:
Benzene
Phenol
Toluene
Butanol
Ethylene dichloride
Methanol
Isopropanol
Carbon tetrachloride
These compounds are a small fraction of the troublesome organic
constituents in the waste stream. Thus, the resulting analysis
of these compounds does not provide conclusive data on the
characterization of this industria 1/municipa 1 wastewater.
Table 78 is a record of parameters monitored at the Deep
Shaft pilot facility during the months, March to July 1977;
Table 79 lists influent monitoring data for the month of May 1977.
The influent stream is monitored daily for the following parameters:
TSS, BODs, soluble BOD5, and COD. Samples are collected by a
composite sampler that siphons incremental aliquots at a predeter-
mined time interval. Figure 38 is a graph of the fluctuating BOD
loading rates; such fluctations indicate the need for a, composite
scanning program in order to estimate average influent BOD loading.
Amenability to Biological Treatment
Characteristics of the Deep Shaft raw influent waste that
could adversely affect biological treatment are:
t High pH values and fluctuations
• Presence of refractory compounds
t Presence of surfactants
208
-------
TABLE 7>?
DEEP SHAFT FACILITY: PARIS, ONTARIO
WEEKDAY (7 DAY) OPERATION
(March 4 - July 15, 1977)
INLET
SBOD5
Whole COD
TSS
AVERAGE
(ppm)
141
53
514
217
RANGE
(ppm)
46
9
216
75
365
138
1264
726
DATA POINTS /134
(days)
94
93
60
92
OUTLET
BOD5
SBOD5
Whole COD
TSS
AVERAGE
RANGE
(ppm)
24
15
89
29
(ppm)
7
1
25
10
- 96
- 56
- 638
- 121
DATA POINTS /134
(days)
95
96
67
94
209
-------
TABLE 79. DEEP SHAFT FACILITY, PARIS, ONTARIO:
MAY 1977 INFLUENT MONITORING DATA (mg/f)
Day
1
2
3
4
5
6
7
Q
(J
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Total
Average
Corrected
Average
SS
124
194
209
229
182
291
218
226
193
176
314
191
233
208
219
177
139
117
208
270
203
456
209
4,886
212
208
BOD5
90
195
Laboratory technician ill
116
Sampler failure
182
180
224
204
-
141
116
195
169
180
213
102
107
102
113
160
167
202
Sampler failure
262
204
3,624
.4 164.7
.5 154.5
Soluble
BOD5
19
84
24
86
86
91
86
43
24
20
92
84
93
114
23
23
20
13
76
77
85
96
92
1,451
63
•
54
COD
238
-
565
531
805
610
479
418
410
652
507
579
698
-
307
224
513
702
582
618
1,264
604
11,292
564.6
»
533.1
May 10-12 Discovered problem with design of flotation tank,
Underflow recycle sump can allow buildup of sludge and prevent
proper sludge removal, Problem was overcome at Paris with
preventative maintenance,
May 10-12 data deleted from corrected average (DFCA).
May 18-24 Exceptionally heavy textile loads (DFCA),
May 31 - Overnight power failure - plant down 8 hours - (DFCA).
210
-------
300
en
E
Z
O
o:
i-
z
m
u
Z
O
u
O
O
CD
200
100
MID
6
AM
NOON
6
PM
MID
TIME OF DAY
BOD MASS LOADING
PEAK* AVERAGE = 1.97
MINIMUM: AVERAGE = 0.14
PEAK* MINIMUM = 14.59
FLOW RATE
••BOD MASS LOADING
ii BOD CONC
Figure 38. BOD loading rates
211
-------
The blending of
in the Paris facility
benefits. One of the
nitrogen (NH3) from t
(orthophosphate) from
to the predominately
benefit is dilution o
in the waste stream.
loading, enzymatic in
membranes associated
tions. Monthly avera
in the Paris influent
reports:
Parameter
BOD5
COD
domestic sewage and ot
influent results in s
se benefits is nutrien
he textile mill efflue
municipal waste and o
carbonaceous chemical
f the high strength in
Dilution may reduce t
hibition, and destruct
with elevated toxin or
ges for the concentrat
were calculated from
her unique wastes
pecific treatment
t balance, in which
nt and phosphorus
ther sources are added
plant wastes. Another
dustrial components
he problems of shock
ion of cellular
heavy metal concentra-
ions of parameters
the May 1977 daily
Avg. concentration
(mg/l)
in influent
164.7
564.6
The ratio of COD to BOD is 3.4, indicating that a portion of the
dichromate oxidizable material is not amenable to rapid degradation
by a biological system. Such a condition is typical of industrial
waste streams, which usually exhibit a COD/BOD ratio of between
3.0 and 6.0.
TREATMENT SYSTEM CONSTRUCTION AND DESIGN
The Paris facility uses conventional construction in addition
to the innovative aeration shaft. This shaft has unique design and
operational structures that differentiate the Deep Shaft facility
from other secondary biological systems. (Figure 39 is a basic
floor plan of the facility.) One unique aspect of the facility
is its minimal land requirement, a fraction of that required by
other types of treatment facilities. This highly reduced land
requirement is an asset, especially where new plant construction
is considered for urban areas.
The head tank and air-flotation tank are housed inside a
structure of three steel trusses and wood framing with a
corrugated metal roof and siding. The structure rests on a 25
steel reinforced concrete slab foundation (Figure 40).» The
housing covers approximately 232 m2 and shelters all equipment
(except the surge tank) necessary for plant operation.
The Deep
limestone and
ft) below the
to a depth of
were used in '
drilling (81.f
cm
Shaft was drilled through alternating layers of
shale; bedrock was found 1.8 to 2.7 m (5.9 to 8.9
surface. A 20.3 cm (51.0 in) pilot shaft was drilled
161.5/m (530.0 ft). Two types of drilling technology
reaming-out" the pilot hole. The initial 30.8 m
cm in diameter) was accomplished with a cable tool
212
-------
Figure 39. Plan view of the Deep Shaft facility
213
-------
3 METAL TRUSSES
SLIDING CORRUGATED
METAL DOOR
HEAD TANK
SURGE TANK
12"
FOUNDATION
(CONCRETE)
LIFT PUMP
(FROM WETWELL)
Figure 40. Sketch of the Deeo Shaft structural housi
nq
214
-------
passes over a weir as the final effluent, which is presently
returned to the headworks of the MOE extended aeration treatment
plant
The Deep Shaft process is a high-rate biological process for
the treatment of biodegradable industrial effluents and municipal
sewage. The process originated from basic aerobic fermentation
technology developed by ICI while researching the production of
single cell protein from methanol (19). The use of air for
both the biological oxidation requirements and the driving force
for liquid circulation is a key to the process. Inherent in the
process is the ability to achieve high oxygen mass transfer
rates compared to conventional aeration processes The shafts
are designed to make maximum use of improved oxygen mass transfer
(19). The same air that is added for BOD removal and circulation
also provides the driving force for solids separation in the
flotation tank.
The Deep Shaft effluent treatment process is essentially a
secondary, plug-flow, complete mix, subsurface aeration basin
utilizing a 155-250 m deep shaft. In all effluent treatment
processes mass transfer is very important with respect to oxygen
and substrate. These concerns are minimized in the Deep Shaft
Process, and the tratment rate is generally governed by the
biodegradability of the substrate. This is accomplished with
better power economy because of high oxygen utilization and
transfer efficiencies. In the Deep Shaft process, the dissolved
oxygen is approximately ten times that in conventional processes.
The highly turbulent flow in the shaft aids in mixing and promotes
highly dispersed substrate growth and oxygen in a uniform suspen-
sion of small biological floe. This may explain, in part, the
high F/M ratio at which Deep Shaft can operate without adversely
affecting flocculation (21). In the Deep Shaft system with a
depth exceeding 100 m (330 ft), the residence time of the bubbles
will be several minutes, and the effect described by Henry's Law
(i.e. greater with increasing depth) is so great that most bubbles
will go into solution in the lower regions of the shaft depending
upon the depth and nature of the waste being treated. Therefore,
all the oxygen absorbed will depend upon the biological metabolic
rate rather than on the physicochemical transfer rate (63).
At the Paris facility, influent waste is taken from the
existing sewage treatment plant after screening and degritting.
The waste stream is introduced into the shaft at the top of a
vertical tube which extends to the bottom of the shaft; the waste
flows down the tube and rises in the annular section between the
type and the shaft lining, the downcomer and riser, respectively
(Figure 41). The waste makes several cycles around the shaft
before a portion passes by gravity into the flotation tank.
215
-------
CROSS-SECTION OF CONDUIT ABOVE THE LOWEST FRESH WATER AQUAFER
STEEL PIPE
CASING
RISER
PORTLAND CEMENT
DOWNCOMER
BEDROCK
CROSS-SECTION OF CONDUIT BELOW AQUIFER(DOUBLE STEEL CASING)
STEEL PIPE
CASING
RISER
PORTLAND CEMENT
DOWNCOMER
Figure 41. Sealing of the Deep Shaft conduit
216
-------
which, because of undersized equipment, later caused problems in
reaching the prescribed depth. The remainder of the pilot
shaft was bored to a depth of 161.5 m (530,0 ft) at a diameter
of 55.9 cm (22.0 in), using rotary drilling procedures (29),
A series of surface casings were used in the upper portion
of the shaft to provide support for the rig during construction
and provide additional protection to ensure the integrity of the
shafts. All cases are grouted to the formation with Portland
cement. Figure 41 shows a simplified top view of the shaft
casing arrangement.
When considering the structural integrity of the shaft, it
is apparent, barring major geologic events, that the construction
techniques and proper subsurface testing and siting should provide
ample protection against accidental contamination of the sur-
rounding groundwater systems. The shaft has a length of 154.8 m
(507.9 ft) and a diameter of 40.6 cm (16.0 in). Infiltration into
the shaft presents another problem to be considered in the design
of the sealing system. Natural groundwaters, in particular
aquifers, may exert hydrostatic pressure greater than integral
pressure of the Deep Shaft and result in a flow into the shaft.
The inherent quality of the high-grade steel shaft coupled with
the reinforcing qualities of concrete should adequately provide
a barrier impervious to leakage in both directions.
The design of this unique bioreactor incorporates state-
of-the-art drilling procedures currently practiced by water well
and oil well drillers all over the world. The final considerations
for drilling methodology and construction materials ultimately
depend on geology of the site. Shaft drilling technology is
not new and correct procedures can be documented at well sites
throughout the world.
Flow Process Description
Figure 42 is a schematic diagram of the Deep Shaft plant
flow. Flow from the industries and the town of Paris enters the
conventional MOE plant and is subjected to primary treatment,
which consists of coarse screening and degritting. After pre-
treatment, ferric chloride is added at a wet well for phosphorus
removal, and the influent is pumped to a splitter box where part
of the flow is drawn off to feed the Deep Shaft facility.
Alkaline pH is neutralized by acid addition, and continuous flow
to the shaft is assured by a surge tank. The flow from the
surge tank is introduced into the shaft at the top of a vertical
tube (downcomer) which extends to the bottom of the shaft. The
flow then returns to the surface in the annular section (riser)
between the downcomer pipe and the shaft casing. The shaft
contents are cycled several times as a portion of the flow is
discharged by gravity to the flotation tank. A chemical flotation
aid is added to the flotation tank influent to improve suspended
solids removal. After solids separation, the treated effluent
217
-------
©
ro
co
>• (fa/m-
FI FLOW INDICATOR
FA FLOW ALARM
FS FLOW SWITCH
FRC FLOW RECORDER
CONTROLLER
STREAM NO,
STREAM DESCRIPTION^
EQUIPMENT NO,
EQUIPMENT DESCRIPTION*
1
2
3
4
5
6
7
8
9
10
1 1
SEWAGE
AIR FLOW
POLYMER FEED
POLYMER MAKE-UP WATER
FLOAT RECYCLE
SINK RECYCLE
WASTE FLOAT
EFFLUENT
POLYMER
FLOTATION FEED
DILUTION WATER
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
1 5
AIR COMPRESSOR
STANDBY AIR COMPRESSOR
ROTAMETER
AIR INJECTION PIPING
DEEP SHAFT
SINK RETURN PUMPS
FLOTATION TANK
FOAM BREAKERS
SLUDGE STORAGE
PARSHALL FLUME
POLYMER FEED TANK
POLYMER MAKEUP TANK
POLYMER FEED PUMP
STANDBY POLYMER FEED PUMP
SURGE TANK
Figure 42. Paris, Ontario Teep Shaft flow diagram.
-------
Activated sludge is recycled from the flotation tank to
the shaft to maintain the bacteria population, and air is
injected into the downcomer to ensure viability of the bacteria
and to provide impetus for circulation (Figure 42). At the
head of the shaft, spent air is exhausted to the atmosphere from
a head tank. After the addition of the polymer, flow from the
shaft is directed to a flotation tank where the solids are removed
The treated effluent then passes over a weir and to disposal as
final effluent.
To start the wastewater circulating, compressed air is
injected at a fraction of the depth in the riser The rising
bubbles induce an upward flow in the liquid column, and because
the average weight of water in the downcomer is greater than
the average weight of water in the riser, circulation begins.
Once circulation is established, air injection is gradually
transferred to the same depth in the downcomer pipe. On larger
shafts eventually all of the air will be injected into the down-
comer pipe. Because of the downward velocity of the liquid, 7 6
to 12.7 cm/sec (3.0 to 5.0 in/sec), and the natural rise
velocity of the air bubbles, 1.93 cm/sec (0.76 in/sec) the air
is drawn down the shaft with the liquid. As the air passes
into the riser, the expanding bubbles drive the flow upwards
before escaping into the atmosphere, thus maintaining the
circulation.
At a velocity of 12.7 cm/second (5.0 ft/sec) the effluent
takes between 3 to 6 minutes to complete each circuit. This
longer-than-usual contact time for each air bubble enables the
bacteria colony to make optimum use of the available oxygen and
partly explains the high oxygen transfer efficiency.
Theories involving the cycling environment of the shaft can
be used to explain lower sludge production in the Deep Shaft. As
influent proceeds down the downcomer, theresulting increase in
hydrostatic pressure results in a substantial increase in oxygen
solubilities. The resulting substrated uptake is a function of
metabolism rather than other physicochemical limiting factors.
The Deep Shaft cycling environment of rapidly changing hydro-
static pressure exerts extreme physiological stresses on the
microbiota resulting in a significant reduction in the production
of biomass. Energy from the enzymatic sequences normally used in
cellular growth and reproduction is shunted off into coping with
the abnormal stresses created by the cycling environment of the
Deep Shaft. Sludge production in the Deep Shaft facilities is
0.25 to 0.50 kg (0.6 to 1.1 Ib) of sludge produced for each
kilogram of BOD removed.
The solids separation phase of the process utilizes dissolved
air bubbling out of solution in the riser to form a sludge blanket
floating on top of the flotation tank. This sludge blanket is
formed by the particles suspended in the rising waste adhering to
219
-------
the small air bubbles. A polymer aid is added to the waste as
it leaves the Deep Shaft to encourage solids separation. The
polymer forms a bridging chain which agglomerates the individual
solid particles and results in a more buoyant floe being produced
in the flotation tank.
The advantage to this flotation system is that both settled
and floated sludges are returned rapidly to the shaft and mixed
with new influent wastes. This is beneficial for an activated
sludge process. Sludge concentrations of 6 to 10 percent are
indicative of luxury thickening in the flotation tank.
The increase is useable oxygen deliverabi1ity and higher
solids concentration in the shaft can result in an aeration
volume reduction of 50 times that of conventional systems. How-
ever, it should be noted that it can cost 10 to 20 times more per
unit volume to install a subsurface Deep Shaft aeration system
rather than an overground structure.
The ICI Deep Shaft aeration process is a high rate process.
Retention times for conventional activated sludge plants treating
a similar flow are usually in the range of 6 to 12 hours or longer.
The Deep Shaft aeration process retention time of approximately
one hour (depending upon the waste) is substantially shorter due
to a combination of factors, including:
• Optimized oxygen intensity
• Efficient utilization of an inexpensive source
of oxygen
• Greatly enhanced contact time
• Enhanced mass transfer due to improved oxygen
s o 1 u b i 1 i ty
• Ability to operate at high solids level in
the shaft
• Excellent mixing.
Another advantage of suspended solids removal using flotation tanks
s performed
ds content
to 10
• in v t, ii >~ i u*jvuni,uyv_ \j i ouo(->ciiucu o u I i u i I CIIIU V a I U o I II y II
is that both solids separation and sludge thickening i
in one process resulting in a denser sludge. The soli
of sludge produced from the flotation tank is about 7 .„
percent, whereas a conventional activated sludge plant may produce
a sludge of 1.5 percent solids. The solids concentration
generated in the flotation tank will vary depending upon the nature
of the substrate but generally appears to be much more concentrated
than in conventional sedimentation systems.
220
-------
OPERATIONAL INFORMATION
Operational monitoring of the Deep Shaft facility consists
of a number of parameters. Figures 43 and 44, copies of the
Paris data sheets, show the exact operational parameters recorded
daily.
The influent into the plant is monitored for flow, temperature,
surface tension, suspended solids, color, and odor. The in-line
operation monitoring consists of volatile mixed liquor suspended
solids (MVLSS), pH, dissolved oxygen, respiration, temperature,
and settleable solids pressure in the shaft
The polymer feed system consists of 1
line to a 2.3 m ^ feed tank An 0.4 percent
(Praestol 423K) is made up every third day.
using a polyethylene tank outfitted with a
(350 rpm). The batch is stirred for 45 min
ferred to the polymer feed tank which is si
supply of the aqueous polymer solution Th
fed into the exit of the head tank. The po
automatic and is regulated by a device loca
flume. This device emits a sonic signal wh
volume of polymer added to the waste stream
this automated system is the integral relat
signal and polymer concentration
2 m^ make-up tank on
solution of polymer
Mixing is accomplished
1-horsepower mixer
utes and then trans-
zed for a three-day
e polymer is then
1ymer feed flow is
ted at the Parshall
ich regulates the
The principal of
i onsh i p of sonic
Sulfuric acid stored in a 1.2 m tank is used for
balancing. The generally alkaline nature of the waste
originates with the industrial contribution. The feed
concentrated acid, on the average, is 20 m £ / m i n and is
to maintain the pH around 7.
pH
stream
of the
sufficient
Depending on the MLVSS concentration in the Deep Shaft,
sludge is wasted in order to maintain the optimal concentrations
to yield maximum BOD and COD reduction.
At present, the Deep Shaft has a designed treatment capacity
of 1.9 x 1 0 ^ m 3 / d a y (0.5 MGD). However, the limiting operation
factor is the flotation tank. The designed capacity of this
unit is approximately 4.7 x 103 m^/day (1 2 MGD'
solid-separation capacities of these facilities
increased to allow for increased waste flows
there fo re , the
would have to be
Operational Advantages of the Deep Shaft Process
Low Capital Cost--
The ICI Deep Shaft Process is expected to cost at least 20
percent less than rival mechanical systems This depends, of
course, upon ease of shaft drilling and raw waste characteristics
221
-------
PARIS DAiLY LOG
DAY HO YR
SEWAGE
TEMPERATURE [ ) °F
SURFACE TENSION I I OTNE3/CM
- D
1C
EFFLUENT
FLOW
I l-»
I I PPN
[ I"-
EFFLUENT
IQO COLOUR I
I ODOUR I
J ] I DYNE3/CM
HLiO TANK MIXED LIQUOR
»» I i
WT. PPM DO
RE3PI RAT I O
N [ JPPM
1CCQ ML. CYLINDER TEST
10 MIN.
ML, FLOAT
ML. 9 INK
DQWNCOMER
RI3E9
02 IN OFF-GA3
HOUR Mis VOL *
'•Il"si°
CRITICAL LOW LIMIT
POLYMER FEE
37ROKE ^ 9IA3 I \% STROKE AT NO PXOu
NT FLOW U3MGD QA I N ^USMGO AT 100^ STROKE
POLYMER PREPARATION
HOUR MtN Iw p.GA L3. %
AUTSHATIC
MANUAL I I PLA
LID EH
TANK FE£D fLOC SIZE
[ I MM. CENTRIFUGE | | HL.
WINQOy 1 WINDOW 2 _W1NOOW ^ WIN0 OW_^_
1000 ML. CYLINOEfl TEST
1 M 1 NUT_e
ML. rLOATj I
ML. 3!NK
'-NO E^ LOW
FRACTION LENGTH
?UMP| JCYCLE3/MIN [^ JUSMGO CENTRtFU^ |ML. RAKE SPEED SETTING NO.
WAS. IMG LARGE MOYNO (33.1
SEC PUMPED
AIR COMPRESSOR
OIL TEMP. |
OIL PRE33.
OIL LEVEL [
HOUR METER
Figure 43. Deep Shaft daily data log.
222
-------
DIGESTOR DAILY LOG
DAY MQ. YR
SAMPLING BEFORE CHARGING
HOUR MtN. SAMPLE NO. MG Og^/-,U?L MO Og/GM VS3/HH PH °C
J_
EZ! CD
CU EH
30LE SCFM
CKAfiGING 3MALL MOVNO (8.3 IGPM)
HR MIN. 3EC SiMP'.E NO. PUHPINO Tlȣ US GiLLOW
MIN. 3CC.
STORAQC INVEMTORY
US GALLONS
J
n
SMALL TANK
aio TANK
SLUDGE RECEIVING
SOURCE PLANT
WCKSHBILL NO.
INTO SMALL
INTO 9iQ TANK
PRIMARY I I SEC. I I MIXED I I
C«PT,E= r,B3T I I >««NCD WH.LE I [ I
1 J OI3CMABOINO | I I
I NCMES PROM TOP F I NAL US OALLOM3
n
TIME
Remarks
TIME
Incidents
Figure 44. Deep Shaft daily digester data log
223
-------
Reductions in surface area requirements for the sewage treatment
plant as typified by the ICI Deep Shaft Process should offer
additional savings associated with land acquisition Advantages
of enclosing the treatment facility may also be easily realized
Low Temperature Operation --
Successful operation of waste treatment facilities at low
ambient conditions is imperative in northern latitudes. The
logistics of building the biological aeration unit underground
and the configuration of the unit allows the system to be
entirely enclosed ensuring good bioreactor temperature control
An enclosed structure offers favorable working conditions all
year round. It was found that an enclosed system is easier to
maintain and is likely to receive better attention, especially
in the winter months. The wastewater temperature will not drop
below the influent temperature, as the influent by the nature
of the process is not exposed to ambient conditions Biological
activity is not impaired, as the influent is never exposed to
ambient conditions, which result in a temperature reducti
and consequent reduction in biological activity
i on
Absence of Obnoxious Odor--
The absence of obnoxious odor is important from an
aesthetic and operations standpoint. The enclosed subsurface
nature and highly aerobic environment in the Deep Shaft Process
results in a facility free from obnoxious odors The gaseous
carbon dioxide generated is vented to the atmosphere directly
from the head tank. This results in a safe working environment.
Minimization of Plant Surface Area--
Minimization of plant surface area is critical to ensure
the lowest possible civil and building costs The small surface
area requirements associated with Deep Shaft results in lower
foundation cost and allows the enclosure of the entire plant to
be considered without incurring large costs
Competitive Operating Costs--
The annual operating cost of the ICI Deep Shaft Process is
expected to be competitive with most other systems The polymer
costs are expected to be offset by aeration horsepower savings
particularly in larger plants
Ease of Operation--
The waste treatment process must be very easy to operate and
must offer a large degree of reliability since the process will
be expected to operate on a semi-attended basis by operators who
224
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may not be technically trained in sewage treatment plant
operation. There are no sophisticated process controls involved
in the operation of Deep Shaft technology. The process is
designed to be operated by personnel with no previous experience
in wastewater treatment and with no special technical skills.
Alarm systems can be included not only to announce shutdown
of operating compressors but also start-up of standby units
automatically. Polymer addition equipment also features liquid
level alarms indicating failure of polymer feed pumps.
Operator responsibilities include periodic sludge wastage,
polymer mixing and routine maintenance of the compression system
plus maintenance of the rakes on the flotation cells. A Parshall
flume is used to measure effluent flow, and a sonic signal is
relayed to the chemical flotation aid feed equipment to ensure
proper amounts of chemical flotation aid are added.
Process reliability in the Deep Shaft is enhanced by the
large oxygen deliverabi1ity and turbulence in the aeration shaft
which results in a capability to buffer 8005 and pH shock loads.
Filamentous organisms can cause severe bulking problems in
conventional biological processes. However, filamentous organisms
can exist in the highly aerobic Deep Shaft; they do not appear to
pose the problems associated with solids separation in conventional
systems. Because of the extensive turbulence, morphology of the
filamentous organisms is greatly changed as they pass through the
shaft.
Sludge Handling and Disposal--
Sludge handling and disposal costs account for approximately
50 percent of the cost of operating a sewage treatment plant.
The ICI Deep Shaft flotation cell produces a solids float of 7
to 10 percent, stabilized by an innovative aerobic digester.
Tests performed by ICI at Billingham, England, have shown
that sludge taken from the ICI Deep Shaft process has a specific
lower resistance to dewatering. At the Paris plant, this is
expected to be further enhanced because of chemicals used to
improve bubble attachment in the flotation cell.
TREATMENT EFFICIENCY
The Paris Deep Shaft Facility has just recently become
operational. The amount of waste data thus far generated is,
therefore, limited. The in-house monitoring program is also
limited in scope. Table 80 shows the influent and effluent
quality monitored during weekends for a three month period, March
to July 1977; Table 81 shows the daily effluent monitoring data
for May 1977. Tables 82, 83, and 84 relate the removal efficiencies
for the parameters being monitored. The removal efficiencies in
225
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TABLE 80
DEEP SHAFT FACILITY: PARIS, ONTARIO
WEEKEND OPERATION
(March 4 - July 15, 1977)
INLET
SBOD5
Whole COD
TSS
AVERAGE
(ppm)
105
24
356
207
RANGE
(ppm)
57
9
204
102
262
96
1264
726
DATA POINTS /39
(days)
30
30
18
30
OUTLET
SBOD5
Whole COD
TSS
AVERAGE
(ppm)
13
7
42
18
RANGE
(ppm)
5-33
1-26
25 - 94
10 - 32
DATA POINTS /39
(days)
33
32
22
33
226
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TABLE 31 . DEEP SHAFT FACILITY, PARIS, ONTARIO:
MAY 1977 EFFLUENT MONITORING DATA (mg/f)
Day
SS
BODr
Soluble BODr
COD
18
32
Laboratory
19
16
21
34
38
52
94
29
14
14
38
37
47
30
32
19
22
19
49
23
42
28
17
17
30
45
876
31
11
32
technician ill
18
19
13
58
56
85
23
15
12
34
32
38
35
19
11
11
11
40
22
39
24
9
8
31
42
748
27.7
20.4
8
22
10
9
8
24
50
39
43
12
4
10
25
19
24
21
6
5
7
9
22
14
24
12
6
7
19
459
17
12.7
42
53
37
37
109
130
121
135
76
50
52
111
97
102
127
62
42
20
45
111
74
102
79
37
29
63
112
2,055
76
66
227
-------
TABLE 32. BOD REMOVAL EFFICIENCY
(NJ
co
Day
1
2
3
4
5
6
7
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
\
Influent concentrations
influent BODc
(mg/£)
90
195
t
116
180
224
204
141
116
195
169
180
213
102
107
102
113
160
167
202
*
262
204
rff. . ... Kg (Ib) BOD Kg (Ib) BOD n ,
Effluent concentrations 3 . ' ' j Removal
BOD5 (mg/i) loaded r*moved efficiency*
out flow = 473 m /day. (%)
11
32
18
58
56
85
15
12
34
32
38
35
19
11
11
11
40
22
39
31
42
(0.12
43 (94.8)
92 (202.9)
55 (121)
85 (187)
106 (234)
97 (214)
67 (148)
55 (121)
92 (203)
80 (176)
85 (187)
101 (223)
48 (106)
H (112)
4R (106)
53 (117)
76 (168)
79 (174)
96 (212)
124 (273)
97 (219)
MGD)
37 (32)
77 (170)
46 (101)
58 (128)
79 (174)
56 (123)
60 (132)
49 (108)
76 (168)
65 (143)
67 (148)
84 (185)
39 (86)
45 (99)
43 (95)
48 (106)
57 (126)
69 (152)
77 (170)
109 (240)
77 (170)
87.7
83.6
83.6
67.8
75.0
58-3
89.4
89.6
82.6
81.1
78.9
83.6
81.4
89.7
89.2
90.3
75,0
86.8
80,7
88.2
79.4
* Average BOD,- removal efficiency based on the record data for the month of May 1977 is 81.9%.
t Blank section in recorded data is due to sampler and power failure.
-------
TABLE 83. COD REMOVAL EFFICIENCY
Influent concentrations Effluent concentrations , , , A Removal
influent COD COD (mg/O loaded , rem°Ved efficiency*
Day (mg/7) flow = 473 rn/day (0.12 HGD) (%}
1
2
3
4
5
6
7
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
238
t
565
531
805
610
479
418
410
652
507
579
698
307
224
513
702
582
618
604
42
109
130
121
135
76
50
52
111
97
102
127
42
20
45
111
74
102
112
113
267
251
381
287
227
198
194
308
240
274
330
145
106
243
332
275
292
286
(249)
(539)
(553)
(340)
(633)
(500)
(437)
(428)
(679)
(529)
(604)
(723)
(320)
(234)
(536)
(732)
(606)
(644)
93
216
190
324
225
191
174
169
256
194
226
125
97
221
280
240
244
234
(476)
(419)
(714)
(496)
(421)
(384)
(373)
(564)
(428)
(498)
(276)
(214)
(487)
(617)
(529)
(538)
82.4
30.7
75.5
85.0
77.9
84.1
88.0
87.3
83.0
80.9
82.4
31 .8
86.3
91.1
91.2
84.2
37.3
83.5
81.5
* Average COD removal efficiency based on the recorded data for the month of May 1977 is 83.9';.
t Blank section in record data is due to sampler and power failure.
-------
TABLE 84. SUSPENDED SOLIDS REMOVAL EFFICIENCY
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Influent
S S (mg/t)
124
194
t
209
229
182
291
218
226
193
176
314
191
233
208
219
177
139
117
208
270
203
209
Effluent
S S (mg/£)
18
32
19
34
38
52
94
29
14
14
38
37
47
30
32
19
22
19
49
23
42
45
Removal
efficiency (*) *
85.5
83.5
90.9
85.2
79.1
82.1
56.9
87.2
92.7
92.0
86.8
80.6
79.8
85.6
85.3
89.3
84.2
83.7
76.4
91.5
79.3
78.5
* Average suspended solid removal efficiency is 83.5%
tBlank section in the recorded data is due to sampler
and power failures.
230
-------
general are in the low 80 percent range for BOD, COD, and
suspended solids At first glance, these results seem low when
compared to treatment efficiencies of conventional activated
sludge systems for industrial wastes The somewhat low values
of removal efficiency can be attributed to the highly fluctuating
influent characteristics of the textile manufacturer
Effects of Wastes on the Receiving Biota
At the Paris plant, sludge was introduced from the on site
conventional S.T.P. It was assumed that its biota would be
acclimated to the type of industria 1/municipa 1 wastewater it
would be treating. It was found that the biota quickly adapted
to the pressure cycling in the Deep Shaft Process. In addition,
there were no problems experienced by the microorganism function-
ing with BOD reductions, and flocculation characteristics
generally stabilized within 24 hours. In general., the micro-
biological populations in the Deep Shaft sewage treatment system
have been found to be very similar to those of the conventional
activated sludge systems. The effects of dilution on the
receiving microbiological population have been favorable Any
potentially toxic compounds inherent in the waste stream seem
to be diluted to a concentration with minimal deleterious effects
on biotic populations. However, this says little about the effect
of the eventual biomagnification of toxic or carcinogenic substances
which might be present in the treatment plant effluent.
Impact on Sludge Handling
Luxury sludge thickening is an integral part of the solid
separation process in the flotation tank. A solids content of
6 to 10 percent is common and occurs without a separate sludge
dewatering process. An innovative sludge stabilization system
has been implemented at the Paris pilot facility, a 7 6 m (3.0 in)
diameter, 152.4 m deep (500 ft), U-tube Deep Shaft aerobic
digester. The operation is entirely experimental, and initial
results indicate that this hybrid digester is capable of
stabilizing raw sludge in one-fifth the time of conventional
aerobic digesters. Documentation, at present, is not available
because presumptive and conclusive testing is not completed.
The impact of these innovative sludge generation and
stabilization procedures could be very significant in reducing
the operational cost of sludge handling. This unique stabilization
process could also have a profound effect on structural cost when
related to costs accrued in construction of conventional aerobic
digesters. The retention time reduction associated with the
Deep Shaft U-tube could reduce the size needed for the structure
of conventional anaerobic sludge digesters; wasted sludge from
the experimental stabilizer and flotation tank is routed into
the headworks of the conventional sewage treatment plant located
adjacent to the pilot plant.
231
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ECONOMIC EVALUATION
The Paris Deep Shaft facility was constructed by CIL for
an initial cost of $400,000 (based on 1976 cost data). This
pilot system was completely financed by ICI. A construction
cost summary is shown in Table 85. These costs were derived
from estimates supplied to SCS Engineers by Eco Research Ltd.
which did not include either the costs associated with the
construction of the building which houses the treatment facility
or those incurred with site preparation for construction.
Estimation of these costs were derived from Means Cost Data , 34th
edition, 1976.
The total estimated 1976 operation and maintenance costs for
the Deep Shaft Facility are outlined in Table 86. A conservative
estimate of maintenance cost was 10 percent of total construction
cost. This relatively small maintenance cost is due, in part,
to the inherent reduced land requirement of this facility
Operation labor and supervision were based upon a staff of one
supervisor and one laborer. Cost of chemicals usage was based
on $3.50/kg ($350/lb) for the polymer supplied by Bayer Chemical
Company and $ 0 . 0 4 / £ ( $ 0 . 0 4 / g a 1 ) for sulfuric acid (price quote
by McKesson Chemical Company, 1976). Power costs were based on
the total horsepower utilized by the Paris pilot facility. The
sludge disposal costs were not included, since this facility
recirculates wasted sludge into the headworks of the MOE
conventional wastewater treatment facility.
The cost of BOD and COD removal is relatively high. The
small volume of wastes being treated and the experimental nature
of the pilot plant facility are major factors contributing
to this elevated cost. A removal cost comparison between this
facility and large scale conventional industrial systems is not
appli cable.
232
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TABLE 85. PARIS, ONTARIO DEEP SHAFT FACILITY:
ESTIMATED CONSTRUCTION COST SUMMARY
Capital investment Cost
Hardv/are - installation $ 283,000
(includes):
a. Air compressor system (2)
b. Sink return pumps
c. Flotation tank
d. Foam breakers
e. Parshall flume
f. Polymer feed tank
g. Polymer make-up tank
h. Polymer feed pump (2)
i. Rotometer
j. Deep shaft
k. Surge tank
1. Acid tank
m. Instrumentation
Building construction - based on ? 63,000
15 x 15 m dimension at $270.00/m
Site preparation 54,000
Total costs $ 400,000
Determined from cost estimates supplied Eco Research Ltd.
Based on 1976 cost.
tBuilding construction cost and site preparation cost was
estimated from Building Construction Costs data 1976, 34th edition.
233
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TABLE 86. PARIS, ONTARIO DEEP SHAFT FACILITY: O&M COST 1976
Costs/yr
Operating labor and supervision* $ 15,000
Chemicals - acid (H2S04 at $0.038/gal) 400
polymer (Prerestol - 423K @$3.50/kg) 4,000
Power (compressor + pump hp) 200
Maintenance (1% of construction) 4,000
Miscellaneous supplies 1,000
Amortize investment 35,000
(20 yrs at 6%)
Total $ 59,600
Cost of kg BOD removed = $2.60/kg ($2.60/lb)
Cost of kg COD removed = $0.70/kg ($0.70/lb)
*
It should be noted that the Deep Shaft Facility does not
require continuous personnel monitoring.
Capital recovery factor = 0.08718. Salvage value not included.
234
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AN EASTERN CHEMICAL
PRODUCTION PLANT UNOX FACILITY
INTRODUCTION
In 1946, a 5.68 x 103 m3clay (1 50 MGD) secondary wastewater
treatment plant was constructed on the grounds of an East Coast
chemical company. Initial secondary treatment processes con-
sisting of trickling filters and activated sludge eventually
produced sufficient odors to cause citizen complaints. Conse-
quently, in 1972, the company installed a UNOX pure-oxygen, bio-
logical system to handle secondary treatment of the influent waste
streams.
Waste streams at the plant are from two sources: 1) sanitary
wastes; and 2) industrial wastes The treatment plant occupies
approximately 1 ha (2.5 ac) of land and treats between 4 9 to 5.7
x 1Q3 m3/day (1.3 and 1.5 MGD). Total hydraulic retention time
available in the UNOX system is 12.7 hours The biological treat-
ment system is aerobic.
Various problems are encountered in conventional biological
treatment of industrial wastes containing highly carbonaceous
and proteinaceous wastewaters. Such difficulties include:
• Varying quantity and quality of organic wastewater
influent to the treatment plant (discharged from a
large chemical complex), resulting in non -equi1ibriurn
conditions
• Synthetic organic constituents inhibitory to nitro-
philic protozoa and flocculating organisms
• Surfactants causing foaming problems.
To assist in the elimination of potential problems, the
designers of the UNOX facility proposed a system with sufficient
volume and suitable hydraulic retention time. Since this system
has to meet a BOD and suspended solids effluent amenable to
further municipal treatment, the primary concern of the treatment
facility is a significant reduction,on an odor-free basis, of
the BOD and suspended solids in the effluent. Consequently, pure
oxygen is used in the UNOX system to reduce large quantities of
organic waste loads and maintain an equilibrium condition
through the system.
235
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Plant History
In April 1972, the chemical plant began operation of the
UNOX process. Before installation of the system, the treatment
plant consisted of primary and secondary treatment with trickling
filters and an activated sludge unit. Odors arising from the
trickling filter prompted neighboring citizens to complain.
Consequently, the chemical company sought a treatment system which
would eliminate the odor as well as reduce the BOD and suspended
solids (SS) that were discharged.
The effluent from the chemical plant enters a municipal
sewerage system and is further treated at the municipal wastewater
treatment plant. Consequently, effluent quality has to meet
the upper limits of BOD of 250 parts per million (ppm) and
suspended solids of 250 ppm. If these criteria are exceeded on
an annual average, the municipality charges the chemical company
an extra 3.3 cents per kilogram of BOD.
The UNOX system was considered for the treatment of the
combined sanitary and industrial waste because it could treat the
wastewaters sufficiently. In addition, a cover on the UNOX treat-
ment system eliminates the odor problem.
The company has been pleased with the cost of operation and
maintenance of the system.
Site Location and Regional Characteristics
The chemical plant, like many others located in the eastern
part of the United States,is nestled in a residential and
commercial area and provides a major source of employment for the
area. These plants generally are located in cities with population
of 10,000 to 20,000 people. Consequently these companies
considerably impact the communities' economy.
The plant is located in a warm temperate climate with moderate
precipitation throughout the four seasons.
WASTEWATER IDENTIFICATION
Waste Sources
The major sources of industrial wastes at the chemical plant
are: fermentation processes, biological and natural extraction
processes, chemical synthesis processes, formulation processes,
research, and sanitary wastes. Discharges from the research
contribute a variety of wastes originating from laboratory
experimental conditions and quality control. The more common
industrial waste discharged into the plant sewerage is the spent
broth from antibiotic manufacturing.
236
-------
Other discharges considered wastewaters include once-
through cooling water, recirculated water and broiler blowdown
These wastewaters are released to waterways and thus are controlled
under the National Pollution Discharge Elimination System Act.
The pond system from which most of these discharges flow has been
revised for use as a spill collection device to prevent accidental
contamination of one of the waterways
The electrical maintenance program of the plant specifies
that transformers containing PCB compounds be sent to outside
contractors for repair or disposal. Waste solvent-containing
aqueous streams from refining, recrystallization or crystal
washing operations are sent to solvent recovery units, and
concentrations of solvents in the still waste and cleanup operations
are limited by policy. Monitoring of these streams by gas/liquid
chromatography methods is mandated Some small volume solvents
are shipped out of the plant for recovery by a contractor.
Occasional contaminated fermentor batches are either dumped
slowly into the sewer or are trucked to the treatment plant where
they are pumped into one train of the UNOX system, and held until
the BOD value is low enough to warrant passing the mixed liquor
back into the system. Either of these procedures is carried out
only after notification of and by permission of the plant
supervisor.
Sequential variations of production and product mix have had
no long lasting nor unfavorable effects on the treatment plant,
except for such factors as primary solids removal (which is
dependent mostly upon the type of influent solids), foaming,
at the secondary stage, and physical effects such as line restric-
tions or blockage. Specifically, the following areas have or
have not affected the treatment plant efficiency.
• No problems have been ascribed to toxicity.
• Shock hydraulic loadings have contributed to
solids overflow from both the primary and
secondary clarifiers during high production
periods. This problem has been lessened by the
inclusion of surge capacity.
• Organic overload shock has been diminished by pro-
longed aeration of the overload material, provided
it can be isolated and trucked to the treatment
plant and the plant design permits isolation of
a portion of the secondary treatment system.
t Certain products contribute to foaming, usually
substances in the influent rather than substances
formed during secondary treatment. Excessive foaming
seems to be controlled by water sprays outside the
237
-------
secondary vessel; control inside the vessel
does not appear feasible at this time.
• Although not pinpointed to a specific pro-
duction, the treatment plant did experience
for two different, but fairly long lasting
periods, filamentous organisms which appeared
to dominate the culture. They had little effect
on the BODc reduction, but made solids removal
difficult because of poor settling and compaction
characteristics imparted to the mixed liquor
The cause of growth acceleration of these organisms
is unknown. The treatment varied with the lowering
of the temperature from the thermophilic to the
mesophilic range to eliminate the first condition
to the minimizing of dissolved oxygen and deliberate
overloading to halt the second condition.
SCHEMATIC AND DESCRIPTION OF SYSTEM
Figure 45 depicts the schematic flow of wastewater through
the treatment plant at the chemical processing plant. The UNOX
system was based on the design parameters of temperature, pH, BOD,
mixed liquor volatile suspended solids (MLVSS), the food to
microorganism (F/M) ratio, and the settling characteristics of
generated siudqe .
The incoming waste load is comprised of industrial waste
with a strength of 1,000 to 3,000 mq/£ BOD and a flow of 3 8 x
103 m3/day (1 MGD), and a sanitary waste with a strength of 100
to 300 mg/l and a flow of approximately 1 1 x 103 m3/day (0 3 MGD)
The combined wastes flow to a pump station through a bar screen
of 2.5 cm (1.0 in) dia. steel bars approximately 2.5 cm (1.0 in)
apart.
Pump Station
The pump station consists of four Demming deep well centri-
fugal pumps which pump the wastewater and return sludge to a
flash mix area where polymer is added. At the pump station, a
stationary crane is used to lift the pumps because of a low level
400 KV line above the pump station The chemical plant has had
problems with the pumps. The pump impellers have been picking up
calcium from lime and the pumps become unbalanced. These pumps
are high maintenance items. From the pump station, the waste
influent is pumped to the flash mixer.
Flash Mixer
The flash mixer is comprised of a polymer addition tank where
an anionic polymer number (835A magnifloc polymer by American
Cyanamid) is added in a concentration of 1 to 2 parts per million
238
-------
IX)
CO
i-D
SHUNT
TANK
SYSTEM
(SPILL
BASINS)
190 in3 EACH
3 SECONDARY CLARIFIERS
12 m DIAMETER
303 Itl3 EACH
BAR
SCREENING
INFLUENT
1000-3000
mg/C BOD
2000-3000
mg/C ss
3. a x io3
m3/DAY
I
FINAL EFFLUENT
POLISHING
<250
LIFE
STATION
AQUEOUS SANITARY WASTE
1.1 X 103 m3/OAY
RETURN SECONDARY SLUDGE
WASTE PRIMARY SLUDGE
DEWATERIZING
RETURN SLUDGE FROM POLISHING
I
SLUDGE
CONDITIONING
SLUDGE THICKENER
.9 m DIAMETER
170 m3
Figure 45. Schematic of wastewater flow through UNOX plant.
-------
via a flash mixing process. From the polymer addition tank the
influent is gravity fed to the cl arif 1 occul ator.
Clariflocculator
The clariflocculator is manufactured by the Walker Process
Equipment Division of Chicago Bridge and Iron Company. The
dimensions of the unit are 18.3 m (60.0 ft) diameter, 3.7 to
4.6 m (12 to 15 ft) depth and 946 m3 (250 gal) capacity. A
skimmer rotates around the clariflocculator- The raw primary
sludge generated by this primary settling process is taken by
Marlow pumps to a sludge conditioning step, followed by vacuum
filtration. The effluent from the clariflocculator flows to
the UNOX treatment tank where it is joined by the recycled sludge
stream containing approximately 1.2 percent mixed liquor suspended
solvents (MLSS). Influent wastes that pose a potential explosion
hazard are d.etected by means of two MSA hydrocarbon analyzers
located in the first stage, and the stream can be diverted to
shunt tanks.
Shunt System
This system has four compartments of 190 m3 gal (5,000 gal)
each which can be used for surge control into the UNOX system.
An electrically controlled 45.7 cm gate (Philadelphia Gear Corp.
Limitorque) can be activated by a signal from the hydrocarbon
analyzer to allow potentially explosive mixtures to flow into
the shunt tank for aeration in open tanks. The shunt tank
capacity represents a conversion of the old activated sludge
system to this storage system in the new plant. The agitators
in the four cells of the shunt tank are maintained in a standby
condition. The cells are interconnected on the bottom and top
and allow the wastewater to be pumped back into the clarifloc-
culator effluent sump which then a.llows it to flow into the UNOX
box.
UNOX System
Figure 46 depicts equipment attached to and incorporated in
the 0.3 m (1.0 ft) thick reinforced concrete UNOX box. The
UNOX box has a capacity of approximately 3,104 m3 (820,000 gal)
and is approximately 4.3 m (14.0 ft) deep; a 3.0 m (1Q. 0 ft)
depth of liquid is maintained, the remaining 1.3 m (4.0 ft) is
used for gas.
The oxygen production and supply system used to supply the
oxygen for the UNOX process is pressure-swing absorption system
(Figure 47). There is an in-depth discussion of the system under
"UNOX Treatment System."
240
-------
FNJ
GAS RECIRCULATION
COMPRESSORS
VALVE PRESSURE SIGNAL
OXYGEN
VENT
OXYGEN
SUPPLY
WASTEWATER
FEED '
RECYCLE
SLUDGE
AERATION
TANK
COVER
STAGE 1
STAGE 2
STAGE 3
MIXED LIQUOR
EFFLUENT TO
CLARIFIER
Figure 46. Schematic diagram of UNOX system.
-------
CLARIFLOCCULATOR
EFFLUENT
\
RECYCLED
SLUDGE
INLET BOX
BAFFLES
BAFFLES
BAFFLES
CAPACITY: 3104 m~
EQUIPMENT LEGEND: - GAS OUJLET
1. OXYGEN INJECTION POINTS - BUFFALO FORGE CO. BLOWERS,
ALLIS CHAMBERS INDUCTION MOTORS: 5 HP, 3530 RPM
2. RODNEY HUNT FLOW REGULATORY GATES
3. LIGHTNING MIXERS - 50 HP IMPELLER MOTORS
4. LIGHTNING MIXERS - 40 HP IMPELLOR MOTORS
5. OLECO, TYPE V-130 VACUUM PRESSURE RELEASE
6. MSA MYDROCARBON ANALYZERS
Figure 47. Flow control and mix inn in the
UNOX system - overhead view.
242
-------
Secondary Clarifiers
The effluent from the UNOX box flows into a flow splitter
box where the flow is diverted to three 12 m (40.0 ft) diameter
secondary, upflow clarifiers each with a capacity of 303 m3
(80,000 gal). Two-thirds of the UNOX effluent flow from the
splitter box enters a manhole which divides the flow by 50
percent for two clarifiers; the other one-third of the flow from
the splitter box goes to the third clarifier. The effluent from
the clarifiers enters a manhole and is distributed to a final
12 m (40.0 ft), 303 m3 (80,000 gal) capacity polishing clarifier
The effluent from the polishing clarifier is then discharged to
the town sewerage system and is further treated in the municipal
wastewater treatment plant.
Monitoring Systems
The treatment plant is principally operated by monitoring
the Dissolved Oxygen (DO) in the UNOX system on the partial
pressure on the walls of the UNOX system. The densttometers are
located in the secondary clarifiers and measure the density of
the sludge. They are operated on a vibrating tuning fork
principal which activates or shuts off a pump depending upon the
thickness (density) of the sludge in the secondary clarifiers.
The monitoring device controls the recycle of the secondary
siudge.
Sludge Handling Facilities
The primary sludge (approximately 12 percent solids)
generated from the clarif1occulator is pumped by variable speed
Marlow pumps to the sludge filtration system, The secondary
sludge is pumped from the thickener to the sludge filtration
system directly or, preferably, mixed with primary sludge for
filtration. Quick lime staked to an 18 percent solution and
alum as a 49 percent solution are added to the sludge in the
conditioning tank. This process thickens the secondary sludge
to about 4.5 percent solids. All the sludge then is processed
by vacuum sludge filters. A quantity of 900 to 2,300 kg/day
(1,985 to 5,072 Ib/day) of quick lime is used and is pumped in
a 18 percent slurry by Slugger diaphragm pumps, The alum is
pumped by Komiine-Sanderson (KS) diaphragm pumps and a BIF piston
pump.
Three types of vacuum filters are currently being used - one
is a 3 x 3.7 m (10 x 12 ft) KS rotary vacuum filter using stain-
less steel springs as media. Other vacuum filters are an Amtak
clothbelt and a 1.8 x 1.8 m (6.0 x 6.0 ft) Eimco clothbelt, The
vacuum pumps are manufactured by Nash The clothbelts are
fastened by Velcro fasteners and are changed weekly. The cloth-
belts are then washed in a solution of 10£ (2.64 gal) of EDTA
(SEQUESTRENE). The solution is then heated to 60° C (140°F) for
243
-------
about two hours and allowed to cool down, after which the cloth-
belts are washed. Approximately every six weeks, the drums are
acid washed using an inhibited hydrocloric acid, trade name
Oakite.
The filtrate from the filters is returned to the flash mix
tank where the polymer is initially added. On the average,
approximately 10 to 12, 3.1 m3 boxes of wet sludge containing
approximately 25 percent solids is disposed every day.
Method of Sludge Disposal
Dewatered waste sludges, including both raw and secondary
combined, are disposed of by composting. The combined sludges
are collected into dumpster boxes and trucked to a composting
area on the plant site. The sludges, sawdust or dried leaves,
and animal manures are available, are piled into windrows
approximately 1.5 m (5.0 ft) at the base and 1.2 m (4.0 ft) high,
but of varying lengths depending upon topography. The windrows
are turned daily during the work week for about a month, during
which time the temperature goes through thermophi1ic temperature
cycle with a maximum of about 60°C (140°F) and the pH drops to
a more neutral range. The individual windrows are then made into
a reserve pile which is made available to the public.
Residual cake from the antibiotic production of Pharma-
ceuticals is also composted. In this process, the cake is simply
aerated by turning daily with a bucket loader for about a month.
The thermophilic cycle is present as with sludge, and the pH
ascends to slightly above neutral. This operation takes place
on a 2.5 ha (6.18 ac) field in the northwest quadrant of the
plant site. The compost is available to the public on a no
charge basis, or is disposed by plowing under in successive 10-
cm (4.0 in) layers on an adjacent 2.8 ha (7 ac) field, or used
as a soil conditioner (as is the sludge compost) on the chemical
plant property itself.
Composting has been a means of sludge disposal for over 20
years, but the success of the operation is dependent upon the
availability of relatively large amounts of land and an expanding
surburban community where willing users are available,
UNOX TREATMENT SYSTEM
The design of the UNOX system is predicated upon pH, COD,
and MLVSS and the settling characteristics of the sludge. The
system operates at a F/M of about .25 and is based upon advanced,
gas-liquid contacting fluid mixing systems design. It is combined
with well established air separation and treatment technology,
which results in an economical supply of enriched oxygen gas
efficiently mixed and dissolved in a mixed liquor of the
244
-------
activated sludge process. Figure 46, a schematic, cross-section
of the surface aerator components of the UNOX system, shows how
the process works at the treatment plant. The aeration tank is
divided into sections or stages by baffles and is completely
covered with a concrete slab to provide a gas tight enclosure.
The liquid and gas phases flow cocurrently through the system.
The feed wastewater, recycled sludge, and oxygen gas are intro-
duced into the first stage.
As shown in Figure 46, the oxygen gas is fed into the first
stage at a slight pressure, approximately 2.5 to 10 cm (1.0 to
4.0 in) of water volume above ambient. The successive aeration
states or chambers are connected to each other in such a manner
as to allow gas to flow freely from stage to stage with only a
slight pressure drop, but sufficient to prevent gas backmixing
or interstage mixing of aeration gas. The liquid flow (mixed
liquor) through successive stages is cocurrent with gas flow.
Effluent mixed liquor from the system is settled in the conventional
manner, and the settled activated sludge is returned to the first
stage for blending with the feed raw or settled sewage.
Figure 47 depicts the general location at the treatment
plant of the equipment used for flow control and mixing in the
UNOX system. The UNOX box itself has a capacity of 3.1 x 103
m3/day (0.8 MGD). The clarif1occula tor effluent and recycled
sludge proceed into the inlet box and then flow through two
regulatory gates into two sections of the UNOX system. The oxygen
injection points are also located at the end of the box where
the influent enters. The flow is then dispersed down both sides
of the box through baffles and mixed by 50-hp and 40-hp motors.
The effluent is then released to the clarifier and the gas is
exhausted off the top (Figure 47).
The associated system for generating the oxygen needed by
the UNOX system is shown in Figure 48. The pressure swing
absorption (PSA) system for oxygen generation is suited to supply
on-site oxygen gas for the smaller wastewater treatment plant.
Main items of equipment are: 1) a feed air compressor; 2) a
PSA unit skid consisting of adsorber vessels, pipe manifolded
to sequencing valves; 3) a cycle control system; and 4) an
instrument air dryer to provide clean dry instrument air.
The PSA system uses three adsorbent vessels to provide a
continuous and constant flow of oxygen gas. The feed air is
compressed by a non-lubricated compressor. As it flows through
one of the adsorbent-filled adsorber vessels, the compressed air
is separated into oxygen and a nitrogen-rich waste stream. The
adsorbent is a granular material (molecular sieve) which attracts
and traps (adsorbs) the carbon dioxide, water, and nitrogen gas,
producing a relatively high purity oxygen product. While one
bed is adsorbing, the other two are at various stages of
regeneration.
245
-------
FEED
AIR
AFTER-
COOLER
PRODUCT
I I
OXYGEN
VAPORIZER J
LIQUID
OXYGEN
STORAGE
COOLING
WATER
ADSORBER
V
H20
ADSORBER
B
ADSORBER
GASES.
PRESSURE SWING ADSORPTION UNIT
Figure 48.
Flow diagram of a "lindox"
PSA oxygen generating system
246
-------
The PSA oxygen generator operates on a compressor-swing,
adsorption concept in which the oxygen is separated from the feed
air by adsorption at high pressure, and the adsorbent is regener-
ated by a blow down to low pressure. The process operates on a
repeated cycle: adsorption and regeneration.
During the adsorption step, feed air flows through one of
the adsorber vessels until the adsorbent is partially loaded
with impurities. At that time, the feed air flow is switched to
another adsorber and the first adsorber is regenerated. During
the regeneration step, the impurities (carbon dioxide, water,
and nitrogen) are cleaned from the adsorbent so the adsorption-
generation cycle can be repeated. Regeneration of the adsorber
is carried out in three basic steps.
• The adsorber is depressurized to atmospheric pressure
to remove some impurities from the adsorbent and to
make it easy to remove the remaining impurities.
• The adsorber is purged with product oxygen to clean
the remaining impurities.
• The adsorber is repressurized to adsorption pressure
and is again ready to separate feed air.
A small instrument air package is also included on the PSA
skid. Since the facility provides its own instrument air, the
only utilities required are electric power and a small amount of
city water for make-up in the closed-loop compressor after
cooling system.
Only the compressor and the automatic control valves require
routine maintenance. Safety is inherently incorporated into the
basic process design: any hydrocarbon contaminar are also adsorbed
on the bed and do not pass through the system with the oxygen
product. The entire system can be started up and shut down in
only a few minutes and operates completely automatically with
only routine plant operator inspection.
OPERATIONAL SAFEGUARDS OF UNOX SYSTEM
1. Safeguards around the UNOX system include monitoring
for explosive mixtures by strategically located hydro-
carbon analyzers that cause alarms to sound and provide
for automatic diversion of the UNOX influent to the
shunt tanks. Severe concentrations of hydrocarbon
may even shut down both the UNOX and PSA systems; such
a shutdown has never occurred.
2 . Foam is controlled by a series of sprays located in
the influent and effluent wells of the UNOX system
and in pits in the discharge line as required. Foam
is piped to the shunt tanks and reprocessed. A backup
antifoam system is in the planning stage.
247
-------
3. The shu.nt tanks are also used for flow surge control
by an automated system. This eliminates solids
overflow from the clarifiers due to high peak flow
periods.
4. Sampling throughout the wastewater treatment
system is carried out using automatic samples and a
timed sequence for a 24-hour period. The parameters pH,
COD, BOD, TSS, and VSS are used more for monitoring
than for control. Special analyses may be run on either
grab or continuous samples as a given situation warrants
OPERATIONAL PARAMETERS OF THE TREATMENT SYSTEM
The treatment plant is operated principally by monitoring
the dissolved oxygen (D.O.) in the UNOX system or the partial
pressure on the walls of the UNOX system. The D.O. is the
principal monitoring parameter in the UNOX system; however, the
partial pressure is used as a backup measurement since the D.O.
probes can become fouled. The densitometers located in the
clarifiers are another important monitoring aid, as they measure
the density of the sludge. The densitometer, operating on a
vibrating principle, senses the density of the sludges and
transmits a signal that activates or deactivates a pump, thus,
in part, controlling the recycle of the secondary sludge, and
restricting overflow of solids from the clarifier.
There are four, 24-hour composite samples in the wastewater
treatment plant at the following locations:
• Just before the flash mixer (raw effluent with solids)
0 After the clariflocculator
t After the secondary clarifiers
• At the final flow measuring device.
Samples are taken at these locations and analyzed daily for
pH, BOD, COD. suspended solids, and total solids. These measure-
ments are then used as additional indications for the operation
of the treatment plant. »
To measure turbidity, the plant has two Hach falling stream
turbidimeters on the secondary clarifier and final effluent
sampling lines.
CLARIFLOCCULATOR PERFORMANCE
^The plant influent passes through the flash mixer where
Magnifloc 835 A (anionic) polymer is added at a rate of 1 ppm and
is then discharged to the clariflocculator During 1975, the raw
248
-------
waste influent flow averaged 4.31 x 103 m3/day (1.1 MGD), with
concentrations of 970 mg/l BODc, 1,780 mg/l COD and 1,090 mg/l
SS.
The clarif1occulator which operates with an average hydraulic
retention time of 5.25 hours provided average BODs, COD, and SS
reductions of 26, 30 and 28 percent, respectively, which
represent 29 percent of the plant BOD re-duction, 38 percent of
the plant COD reduction, and 37 percent of the plant SS reduction.
These data are summarized in Table 87.
UNOX System Performance
During 1975, the UNOX system average influent flow was 4.3
x 103 m3/day (1.1 MGD) with average concentrations of 715 mg/l
BOD, 1,240 mg/l COD and 790 mg/l SS (Table 88). The UNOX system
and secondary clarifiers provided BODs, COD, and SS reductions
of 86, 58, and 52 percent, respectively. These UNOX system
reductions represented 95 percent of the plant BOD reduction,
74 percent of the plant COD reduction, and 68 percent of the plant
SS reduction. Effluent from the secondary clarifiers, prior
to the final "polishing" has concentrations of 90 mg/l BOD and
suspended solids (250 mg/l may be discharged to the town plant
without surcharge). As a result, final "polishing" clarification
is necessary for additional solids removal. Table 89 shows
overall plant performance.
Waste treated by the UNOX system has an average hydraulic
retention time of 7.45 hours and a corresponding solids retention
time or sludge age of 9.6 days. This system is operated with a
mixed liquid suspended solids concentration of 9,250 mg/l ,
with a 75 percent volatile fraction. The biomass loading of
the influent to the UNOX system is FBOD5/M^O.14* and FCOD/M=0.25**
The average organic loading is 10 kg BOD/nwday
Recycle from secondary clarifiers has an average solids
concentration of 22,200 mg/£ (2.2 percent) at a recycle flow
rate of 4.4 x 103 nWday (1.2 MGD) (102 percent of UNOX system
influent flow). Sludge is wasted from the bottoms of the
secondary clarifiers with an average solids concentration of
33,300 mg/l (3.3 percent) at a rate of 11,200 gal per day.
Discussion of the operation and performance of the UNOX
system at the chemical plant must take into account that the
wastewater treatment plant as a whole was designed to pretreat
*FBOD5/M=kg BOD5/kg mixed liquor volatile suspended solids
(MLVSS) per day
**FCOD/M=kg COD/kg mixed liquor volatile suspended solids
(MLVSS) per day
249
-------
TABLE 87. CLARIFLOCCULATOR
Parameter
1975 Average
Range
Clariflocculator
(plant)
Influent
Parameters
Clariflocculator
Operating
Parameters
Clariflocculator
Effluent
Parameters
Flow
BODr
b
COD
SS
BODC reduction
b
COD reduction
SS reduction
BOD,-
b
COD
SS
4.31 x 103 m3/day
(1.1 MGD)
970 mg/C
1780 mg/^
1090 mg/^
26 percent
30 percent
28 percent
715 mg/f
1240 mg/t
790 mg/7
3.4-4.7 x 103
(0.9-1
700-1200 mg/f
1000-2700 mq/Jt
620-2200 mq/t
0-47 percent
3-50 percent
0-68 percent
380-1300 mg/£
560-2700 mq/C
240-2800 mg/i
m /day
.2 MGD)
250
-------
TABLE 88. UNOX SYSTEM
UNOX System
Influent
Parameters
UNOX System
Operating
Parameters
Parameter
Flow
BODg
COD
SS
FBOD5/M*
FCOD/M**
Organic Loadings
(kg BOD/m3/day)
Hydraulic
Retention Time
SRT (Sludge Age)
MLSS
MLVSS
Recycle Flow
Recycle SS
Waste Sludge-
Flow
Waste Sludge-
Solids
BODr Reduction
1975 Average
4.3 x 103 m3/day
(1.1 MGD)
715 mg/£
1,240 mg/£
795 mg/t
.14
.25
10
7.45 hrs
9.6 days
9,250 mg/£
6,875 mq/£
4.4 x 103 m3/day
22,200 mq/i
(2.2 percent)
42.4 m3/day
(11,200 gal/day)
33,300 mq/l
(3.3 percent)
86 percent
Range
3.4-4.7 x 103 m3/day
(0.9-1.2 MGD)
380-1,300 mg/t
560-2,700 mg/£
240-2,800 mq/t
0.07-0.23
0.10-0.38
5.1-18.3
4.0-9.2 hrs
6-50 days
(generally 8-24 days)
4,200-15,000 mg/£
3,500-9,800 mg/l
3.7-5.5 x 103 m3/day
14,000-40,000 mg/£
5.3-113.6 m3/day
' (1 ,400-30,000 nal/day)
26,000-50,000 mq/t
81-91 percent
*F
BOD5 kg BODr influent per day per kg mixed liquor volatile suspended
M solids (MLVSS) in UNOX system
**FCOD = kg COD influent per day per kg mixed liquor volatile suspended
~M~~ solids (MLVSS) in UNOX system
251
-------
TABLE 88 (continued)
UNOX System
(secondary
clarifier)
Effluent
Parameters
Parameter
COD Reduction
SS Reduction
BOD5
COD
SS
1975 Average
58 percent
52 percent
100 mg/l
550 mg/£
380 mg/l
Range
24-81 percent
17-87 percent
200-220 mg/l
200-15,000 mg/£
60-16,000 mg/l
252
-------
TABLE 89. PLANT SUMMARY
Plant
Influent
Plant
Operating
Plant
Effluent
Parameter
Flow
BOD,-
0
COD
SS
BODr Reduction
b
COD Reduction
SS Reduction
BOD5
COD
SS
1975 Average
4.3 x 103 m3/day
(1.1 MGD)
970 mg/t
1,780 mq/C
1 ,090 mg/f
91 percent
78 percent
76 percent
90 mg/f
390 mg/t
260 mg/t
Range
3.4-4.7
700-1,200 mg/t
1,000-2,700 mg/t
380-1 ,300 mg/H
86-95 percent
67-86 percent
32-94 percent
50-210 mg/t
180- 1,200 mq/C
50-500 mg/t
253
-------
variable, high strength industrial wastewater prior to discharge
to a municipal wastewater treatment system. As a result, the
UNOX system is operated with a relatively high mixed liquor SS
concentration and relatively low F/M ratios in order to
accommodate the variable nature of the influent wastewater.
Similarly, the recycle flow from the secondary clarifiers to the
head of the UNOX tank is generally equal to or greater than 100
percent of the flow of wastewate-r influent to the UNOX system.
This high percent recycle helps to maintain the large concentrations
of MLSS desired, increase the solids retention time (sludge age),
and reduce the opportunity for the highly oxygen demanding wastes
sent to the secondary clarifiers of becoming anaerobic prior to
being recycled.
The UNOX system efficiencies were analyzed by plotting BOD
and COD percent removals and effluent concentrations vs. the
respective F/M ratios as well as solids retention times (sludge
ages) as seen in Figures 49 through 52. The data for each
respective graph is given in Tables 90 through 93. Generally,
the highest percent removals of BOD from the wastewaters influent
to the UNOX system occurred as sludge ages increased and F/M
ratios decreased. Effluent quality in terms of concentrations
of BOD, COD, and SS discharged from the secondary clarifiers
improved (concentrations discharged decreased) as solids retention
times increased and F/M ratios decreased. No relationships
appear to exist for the percent removal of suspended solids by the
UNOX system.
It is impossible to identify the optimum F/M ratios for
maximum BOD and COD percent removals, because of variations in
data. However, it is apparent that the percent removal of COD
deteriorates significantly at FCOD/M ratios greater than 0.3 or
sludge ages of less than 10 days. Similarly, there appears to
be a slight reduction in the percent removal of BOD at FBODR/M
ratios greater than 0.2 and again with sludge ages of less than
10 days.
These F/M ratios, at which removal efficiencies and effluent
quality begin to deteriorate, are somewhat lower than anticipated.
In general , UNOX systems for industrial wastes are designed to
operate at FBOD/M ratios of between 0.2 and 0.8. In terms of
sludge ages, deterioration of percent removals and effljuent
qualities at sludge ages of less than 10 days seem somewhat low
since most industrial pure oxygen systems operate with sludge
ages between 8 and 20 days.
ECONOMIC EVALUATION
Construction and operation and maintenance cost information
for a hypothetical UNOX system for processing industrial-chemical
wastewater was provided by Union Carbide Corp. Design assumptions
used in the development of this cost information are shown
254
-------
O PERCENT REMOVAL VS. F/M
BOD
• PERCENT REMOVAL VS. F/M
COD
90
80
70
a*
g
UJ 50
QL
\-
z
UJ 1- U — •
u
(T
UJ
d
30
20-
10
0 °
i
_
-
O
o o
V
• *
) 9
O
. .
*
M
•
0.1
0.2
0.3
0.4
F/M
BOD5
COD
Figure 49.
UNOX system removal efficiencies
(MLVSS used in F/M calculations)
255
-------
O PERCENT BOD5 REMOVAL VS. SLUDGE AGE
• PERCENT COD REMOVAL VS. SLUDGE AGE
100
80
70
60
UJ 50
QL
I-
Z
UJ 40
u
tu
Q_
30
20
10
10
15
»0
SRT =
DAYS
SOLIDS RETENTION TIME
(SLUDGE AGE)
Figure 50.
UNOX system removal efficiencies
BOD5 and COD vs. sludge age.
256
-------
o
•
EFFLUENT BOD,, VS. F/N1 ^
5 BUD,
EFFLUENT COD VS. F/M
1400'
1200-
1000-
\
800-
D
C
z
LU
D
_!
IL
LL
HI
600-
400-
200-
COD
O
0. 1
0. 2
F/M
F/M
0. 3
0. 4
BOD5
COD
Figure 51. UNOX system effluent quality vs. F/M ratio
(MLVSS used in F/M calculations).
257
-------
O EFFLUENT BOD VS. SRT
• EFFLUENT COD VS. SRT
EFFLUENT SS VS. SRT
1400-
5 10 DAYS 15 2°
SRT - SOLIDS RETENTION TIME
(SLUDGE AGE)
Figure 52. UNOX system effluent quality vs. sludge age.
258
-------
TABLE 90. DATA ON F/M RATIOS AMD CORRESPONDING PERCENT
REMOVALS AS PLOTTED IN FIGURE 49
FBOD5/M % BOD5 Removal
.069 87
.094 88
.111 91
.117 90
.132 85
.160 84
.161 83
.168 90
.171 87
.210 83
.233 81
FCOD/M % COD Removal
.102 59
.138 66
.175 58
.177 80
.180 67
.258 52
.260 73
.297 72
.322 39
.371 47
.379 47
259
-------
TABLE 91. DATA ON SLUDGE AGE AND CORRESPONDING
PERCENT REMOVALS AS PLOTTED IN FIGURE 50
Solids Retention Time
(Sludge Age)
5.9
7.8
8.0
8.1
10.0
12.7
17.3
17.3
17.3
23.9
49.7
% BOD5
Removal
83
84
83
81
90
85
90
88
87
91
87
% COD
Removal
47
52
47
39
73
67
58
66
72
80
59
260
-------
TABLE 92. DATA ON F/M RATIOS AND CORRESPONDING
EFFLUENT QUALITIES AS PLOTTED IN FIGURE 51
F /M Effluent
BOD5/M BOD5 (mg/l)
069 47
094 62
111 57
117 42
1 32 99
160 91
161 158
168 62
171 111
201 212
233 124
r /M Effluent
rCOD/M COD (mg/l)
.102 229
.138 257
.175 286
.177 200
.180 296
.258 425
.260 249
.297 397
.322 550
.371 1189
.379 1077
261
-------
TABLE 93. DATA ON SLUDGE AGE AND CORRESPONDING
EFFLUENT QUALITIES AS PLOTTED IN FIGURE 52
Solids Retention Time
(Sludge Age)
5.9
7.8
8.0
8.1
10.0
12.7
17.3
17.3
17.3
23.9
49.7
Effluent
BODC (mg/£)
3
158
91
212
124
62
99
42
62
111
57
47
Effluent
COD (mg/£)
1077
425
1189
550
249
296
286
257
397
200
229
262
-------
in Table 94. Additional estimates for sludge disposal costs and
miscellaneous supplies were deriived from Hovious et al . (59) and
updated to 1976 costs.
Table 95 shows the estimated 1976 construction costs for
the system. The total cost, including contractor and engineering
design services and construction contingencies is $2,113,000 for
a 5.68 x 103 m3/day (1-5 MGD) plant, amortized over 20 years at
six (6) percent to yield a total investment of $184,000. This
investment and estimated operation and maintenance costs are
shown in Table 96. Operating labor is based on one operator
per shift. Power requirements include electric motor drive
for mixing in the UNOX tank and operation of the oxygen generation
plant.
The specified flow and influent and effluent BOD concentration
data shown in Table 89 were used to determine the quantity of BOD
removed per year. This information was used in association with
the total operation and maintenance cost of $437,800/year to
derive a cost of $0.15/kg ($0.15/lb) BOD removed for the UNOX
system. The total treatment costs for the facility have been
estimated at $0.55/kg BOD removed. This figure represents
costs for primary treatment, the UNOX system, allowance for down-
time, and for further disposal of effluents or sludge.
263
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TABLE 94. DESIGN ASSUMPTIONS UTILIZED I
DEVELOPMENT OF UNOX SYSTEM COSTS
Flow: 5.68 x 1O3 m3/day (1.5 M6D)
influent BOD: 1,500 mg/C
influent suspended solids: 1,000 mg/C
COD/BOD ratio: 1.5
retention time: 18.4 hrs
F/M ratio: 0.4
MLVSS: 4,900 mg/C
recycled solids: 2.9%
3 2
overflow rate: 18.3 m /day/m
oxygen supply: 11.8 t (13.0 tons)
oxygen utilization: 82%
dissolved oxygen: 5.0 mg/C
effluent BOD: 120 mg/C
264
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TABLE 95. UNOX FACILITY:
ESTIMATED CONSTRUCTION COSTS - 1976*
Equi pment
Labor
Materials
Contractor overhead and profit
Engineering design services
Total Installed Cost
Conti ngency
TOTAL
$ 883,000
314,000
320,000
$1 ,517,000
142,000
249,000
$1,908,000
205,000
$2,113,000
*Includes secondary clarifier, a three-stage UNOX tank
(50.2 m x 16.7 m; 5.2 m sidewater depth and 0.75 m
freeboard, and oxygen generation equipment. Does not
include primary clarifier, sludge handling equipment,
buildings, or off-site electrical service.
265
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TABLE 96. UNOX SYSTEM:
ESTIMATED O&M COSTS - 1976
Operating Labor $ 20,000
Power (HP x 77.78)**
Mixing 13,500
02 generation 20,000
Maintenance 42,300
(2 percent of construction)
Misc. Supplies*** 1,000
Sludge Disposal*** 157,000
(BODr x $ 0.034/kg BODr x
10% annual inflation since 1971)
Amortize Investment**** 184,000
(20 yrs at 6 percent)
TOTAL $437,800
*This estimate is for the UN^X System only, and does not
include costs for primary treatment, allowance for down-
time, or costs for effluent or sludge disposal.
**From aeration and power cost data at 40-Acre facility.
***From 1971 data presented in reference
****Capital recovery factor = 0.08718. Salvage value not
included.
266
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SECTION V
SAMPLING ACTIVITIES
INTRODUCTION
During the initial phase of this study, four sites were
visited to evaluate design and operational data at facilities
successfully treating organic industrial wastes. The four sites
were:
• Washburn Tunnel Facility, Pasadena, Texas:
5 3
This 1.7 x 10 m /day(45 MGD)completely mixed activated
sludge facility treats wastes from a kraft paper mill
(70 percent) and four petrochemical plants with BOD and
COD loadings of 57,173 and 202,344 kg/day (126,045 and
446,169 1b/day) ,respectively. BODs and COD removal effi-
ciencies were 91 and 70 percent. Phenols and oil and
grease were also significantly reduced during the 17-hr
period in the system.
• 40-Acre Facility, Texas City, Texas:
The 40-Acre Facility, a lagoon system on the Gulf Coast,
employs anaerobic-microaerobic-aerobic-facul tative treat-
ment to process a mixed petrochemical waste flow of
approximately 5.3 x 104 m3/day (14.0 MGD). The plant
actually covers 64 ha (160 ac). Lagoon volume amelior-
ates shock loading effects. The system, which has been
highly successful in reducing marginally degradable orga-
nic material, has a possible 22-day retention time. It
treats BODs loading of 26,100 kg/day (57,550 Ib/day) and
COD loading of 50,438 kg/day (111,197 Ib/day) with BOD5
and COD removal efficiencies of 96 and 76 percent, res-
pectively.
• Deep Shaft Facility, Paris, Ontario:
Costs of the Deep Shaft system are low in terms of oxy-
gen transfer and site area requirements. The Paris
facility treats a waste stream from a variety of indus-
tries; average flow is 4.73 x 1O2 m3/day (0.13 MGD),
267
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with BODs loading of 78 kg/day (172 lb/day)and COD load-
ing of 253 kg/day (558 lb/day),with BOD5 and COD removal
efficiencies of 82 and 82 percent, respectively.
• UNOX Pure Oxygen System:
The UNOX system treats wastes from a chemical manufactur-
ing plant; flow averages 4.3 x 1Q3 m3/day (1.14 M6D) ,
BODs loading of 3,075 kg/day (6,780 Ib/day) and COD
loading of 5,332 kg/day (11,760 Ib/day), with reported
BOD5 and COD removal efficiencies of 95 and 74 percent,
respectively -
The case studies included acquisition of all available data
for the following areas:
• Influent effluent waste stream constituents and overall
treatment efficiency
• Overall plant design and operational details
t Design and operational details for specific plant com-
ponents used for enhancing biodegradation
• Organic wastes not amenable to biodegradation
0 Impact of treatment plant effluents on environment
• Unique or specially acclimated in-plant biota capable
of degrading refractory organic materials
• Cost and energy demands for plant construction, opera-
tion, and maintenance-
As expected, different quantities and types of information
were available at each of the four plants. Both qualitative and
quantitative determinations of hazardous organic wastes in the
waste streams were generally lacking. Gross measurements of
organic materials such as chemical oxygen demand (COD), biochem-
ical oxygen demand (BOD), and total organic carbon (TOC) are of
limited value in evaluating biological treatment of specific
hazardous organic materials.
The efficiency of biodegradation of specific problematic
organic wastes must be measured in terms of complete oxidation
or biochemical alteration of the substrate into substances no
longer considered either environmentally hazardous or toxicologi-
cal. Removal of such wastes in an unaltered state through adsorp-
tion into settleable biological floes may result in significant
removal from the aqueous waste stream, yet the sludges produced
by the treatment process may exhibit the hazardous properties of
the removed constituents and cause sludge disposal problems.
268
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Since the sludge particles of secondary biological waste treat-
ment systems are essentially organic, they can provide substrate
for adsorption of colloidal or dissolved organic hazardous wastes
It is suspected that this phenomenon may be important when com-
paring various treatment alternatives.
The two major goals of the second phase of this project were
to determine:
• The efficiencies of different biological treatment sys-
tems in removing hazardous organic materials from waste
streams
• The mode of removal of hazardous organic materials by
different biological systems, either via biodegradation
or in association with secondary sludges.
In addition to these goals, Phase Two was designed to:
• Identify and characterize the microbial populations in
the biological systems studies
• Determine the environmental sink of specific organic
materials discharged with the plant effluent.
Section V presents the specific sampling activities and the
sampling results for the individual case study sites. Appendix
B presents the rationale for the selection of the organic and
biological parameters measured and the sampling stations and fre-
quency, as well as the sampling and analytical methods.
Due to proprietary considerations, sampling was not possible
at the UNOX pure oxygen treatment plant.
SPECIFIC SAMPLING ACTIVITIES AND RESULTS
40-Acre Facility
The 40-Acre Facility in Texas City, Texas is a lagoon sys-
tem treating predominately petrochemical wastewater. The 64-ha
(160-ac) facility includes pH adjustment (HC1), nutrient addition
(H3P04,NH3), equalization, two anaerobic lagoons, one limited
aeration lagoon, two aeration basins, and two quiescent faculta-
tive lagoons, Flow ranges from 49 to 57 x 103 m3/day (12.9 to
15.1 gal/day).
Samples were taken at 40-Acre for four days, December 15 to
18, 1977. During the sampling period, the wastewater treatment
scheme consisted of equalization, limited aeration, parallel
flow through the aerated stabilization basins, settling in facul-
tative lagoon #1 and discharge to the Hurricane Levee Canal. A
269
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characterization of the facility influent-effluent loading values
for conventional parameters for the sampling period is shown in
Table 97.
Sampling Sites and Frequency--
Figure 53 shows the sites selected for sampling at the 40-
Acre Facility, and Table 98 lists both organic and biological
samples taken, their location, and sample identification desig-
nation. The following discussion explains the selection of the
sampling sites.
Four waste streams are treated at 40-Acre. Influents A, B,
and C enter the system at influent point 1 and influent D at
influent point 2 (Figure 53). Influents A and C (40-A-ORG-COMP-
II) were composite-sampled at a confluent wet well at influent
point 1. Piping for influent B did not allow composite sampling
of influent B and the other waste streams entering at influent
point 1. Fortunately, a draw-off spigot had been installed in
the influent B pipe. Daily grab samples from this spigot were
proportioned using daily flow data and mixed with the 40A-ORG-
COMP-1I composite sample. Influent D (40A-ORG-COMP-2I) was com-
posite-sampled at the influent wet well to the aeration basins.
Samples were taken from the limited aeration basin effluent
(40A-ORG-COMP-3E) and settled sludge (40A-ORG-COMP-6) , and the
waste flows from both aeration basins (40A-ORG-COMP-4E) . A sin-
gle grab sample was taken for the organic analysis of the sludge
from the facultative lagoons (40A-ORG-COMP-7) . A portion of the
GCWDA daily effluent composite sample was used for organic analy-
sis (40A-ORG-COMP-5E).
Sediment samples for organic analyses were grabbed from the
Hurricane Levee Discharge Canal with the La Motte Dredge: one
at the 40-Acre effluent outfall (40A-ORG-COMP-2B) and one up-
stream of the outfall (40A-ORG-COMP-1B) . Approximate sampling
locations are shown in Figure 53.
Biological samples for the microbial population study were
grabbed from various lagoons. All the lagoons active in the
treatment chain were sampled, as well as two inactive lagoons,
one facultative, the other anaerobic. Facultative lagoon #2
(40A-B10-GRAB-5S) and anaerobic lagoon #2 (40A-B1O-GHAB-1S) had
been inactive for 3 and 8 mo, respectively.
Chemical Analyses Results--
The results for the organic analyses of the samples taken
at the 40-Acre Facility are presented in Tables 99 through 101.
The sample designations used in these tables are based on station
location and are explained in Table 98 and shown in Figure 53.
Table 99 shows the organic chemical constituents present in
the two influent sources to 40-Acre (40A-ORG-COMP-1 I and 21);
270
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TABLE 97. CHARACTERIZATION OF 40-ACRE WASTEWATER AND EFFLUENT
LOADING IN KG/DAY (LB/DAY) FOR THE SAMPLING PERIOD
Wastewater
Characteristic
Wastewater
Loading
Effluent
Loading
Percent
Removal
Flow x 104 m3/day (MGD)
TOC
COD
BOD
TSS
VSS
NH3-N
Phenol
5.3 (13.9)
15,396 (33,871)
46,241 (101,730)
22,922 (50,428)
14,134 (36,095)
3,829 (8,424)
339 (746)
25.2 (55.4)
5.0 (13.2)
2,979 (6,567) 81
9,283 (20,466) 80
1,850 (4,070) 92
1,830 (4,026) 87
1,395 (3,069) 64
256 (563) 25
1.13(2.49) 96
271
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(VI
SAMPLE LEGEND
1 COMPOSITE FOR ORGANIC ANALYSIS
2 GRAB FOR ORGANIC ANALYSIS
3 GRAB FOR BIOLOGICAL ANALYSIS
<) SEDIMENT GRAB FOR ORGANIC ANALYSIS
HURRICANE LEVEE DISCHARGE CANAL Qt)
AERATED STABILIZATION
BASIN »2
INFLUENT
POINT »1
EMERGENCY
PILL BASIN
ANAEROBIC LAGOON HI
^
EQUALIZATION
-- BASIN
ANAEROBIC LAGOON «2
H
LIMITED AERATION BASIN
X}..
:
OFFICE AND
LABORATORY
AERATED STABILIZATION
BASIN 11
INCOMPLETE
FACULTATIVE
LAGOON
FACULTATIVE
LAGOON
FACULTATIVE
LAGOON
Figure 53. GCWDA 40-Acre Facility layout and sampling sites.
-------
TABLE 98. 40-ACRE FACILITY ORGANIC AND BIOLOGICAL SAMPLES
LOCATIONS AND IDENTIFICATION DESIGNATIONS
A. Samples for Organic Analysis
LOCATION
Influent to equalization basin
Influent to aeration basins
Effluent from limited aeration basin
Effluent from aeration basins
Effluent from facultative lagoon
Sludge from limited aeration basin
Sludge from facultative lagoon
Sediment upstream of outfall
Sediment at outfall
DESIGNATION
40A-ORG*-COMP*-1I
40A-ORG-COMP-2I
40A-ORG-COMP-3E
40A-ORG-COMP-4E
40A-ORG-COMP-5E
40A-ORG-COMP-6
40A-ORG-COMP-7
40A-ORG-COMP-1B
40A-ORG-COMP-2B
B. Samples for Biological Analysis
LOCATION
Anaerobic lagoon #2
Limited aeration basin
Aeration basins #1 & #2
Active facultative lagoon
Inactive facultative lagoon
DESIGNATION
40A-BIO*-GRAB*-1S
40A-BIO-GRAB-2S
40A-BIO-GRAB-3S
40A-BIO-GRAB-4S
40A-BIO-GRAB-5S
Notes.
ORG - organic analysis samples.
COMP - composite samples taken according to Sampling Methods.
BIO - biological samples for microbial analysis.
GRAB - grab samples taken according to Sampling Methods.
273
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TABLE 99. RESULTS OF GC ANALYSIS OF COMBINED EXTRACTS OF
BASE/NEUTRAL AND ACID FRACTIONS ISOLATED FOR 40-ACRE SAMPLES
(concentration values in pg/1, with no entry representing
concentrations below detection limits)
Samples (40A-ORG-COMP-)
Constituent II 21 3E 4E 5E 6
Halogenated Aliphatics
Bis (2-chloroethoxy) methane 8.0 25.0 1.0
Ethers
Bis (2-chloroisopropyl) ether 16.0 2.0 -
Chloroethyl ether 1.0
4-Bromophenyl ether 7.0 - - - -
Monocyclic Aromatics
Nitrobenzene 58.0 3.0 14.0 -
2, 6-Dinitrotolvene 0.2 2.0 - 3.0 - 0.2
2, 4-Dinitrotolvene 8.0 12.0 2.0 - 0.4 0.2
Hexachlorobenzene - 4.0
1, 2-Dichlorobenzene 0.3 _____
Phenols and Cresols
Phenol 2.0 1.0 - - - 0.4
4-Nitrophenol - - - - 1.0
Pentachlorophenol - 4.0
p-chloro-m-cresol
2-Chlorophenol
Phthalate Esters
Dimethyl phthalate
Di ethyl phthalate
Dibutyl phthalate
Butyl benzyl phthalate
Bis (2-ethylhexyl) phthalate
Polycyclic Aromatic Hydrocarbons
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benzo(b) fluoranthene
Benzo(a) pyrene
Benzo(a) anthracene
7.0
0.6
6.0
4.0
13.0
0.5
3.0
13.0
0.6
4.0
1.0
0.6
8.0
2.0
1.0
6.0
60.0
1.0
2.0
4.0
16.0
1.0
2.0
3.0
12.0
3.0
40.0
21.0
19.0
6.0
26.0
47.0
6.0
4.0
1.0
6.0
1.0
5.0
4.0
0.2
3.0
1.0
0.4
2.0
1.0
0.2
1.0
1.0
0.4
12.0
1.0
4.0
2.0
1.0
2.0
1.0
2.0
1.0
0.2
0.2
1.0
3.0
0 4
274
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TABLE 99 (continued)
Samples (40A-ORG-COMP-)
Constituent II 21 3E 4E 5E 6
Pesticide
Isophorone 15.0 3.0 1.0 2.0 1.0 1.0
PCB's and Related Compounds
2-Chloronaphthalene 0.9 19.0 18.0 - - 0.4
Nitrosamines and Other N-Compounds
1, 2-Djphenylhydrazine 73.0 5.0 27.0 14.0 0.4 0.4
Nitrosodiphenylamine - 3.0 - 1.0 0.2
Benzidene 1.0 12.0 32.0 7.0 8.0 5.0
275
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TABLE 100. RESULTS OF GC/MS ANALYSIS OF
40-ACRE SLUDGE SAMPLE: 40A-ORG-COMP-7
(concentration values in yg/1)
Constituent Concentration
Halogenated Aliphatics
Bis (2-chloroethoxy) methane 4.0
Dichloromethane 12.0
1, 1-Dichloroethene 3.0
1-Dichloroethene 0.5
Trichloromethane (chloroform) 32.0
1, 1, 2, 2-Tetrachloroethane 0.9
Trichloroethene 0.6
Ethers
Bis (2-chloroisopropyl) ether 11.0
Monocyclic Aromatics
Nitrobenzene 3.0
2, 4-Dinitrotoluene 20.0
2, 6-Dinitrotoluene 1.0
Benzene 35.0
Toluene 5.0
Phenol and Cresols
Phenol 10.0
2, 4-Dimethylphenol 1.0
4-Nitrophenol 14.0
Phthalate Esters
Dimethyl phthalate 3.0
Dibutyl phthalate 1.0
Butyl benzylphthalate 5.0
Dioctylphthalate 15.0
Polycyclic Aromatic Hydrocarbons
Naphthalene 4.0
Acenaphthylene 70.0
Acenaphthene 2.0
Fluorene 20.0
Phenanthrene 4.0
Fluoranthene 11.0
Pyrene 3.0
Benzo(a) pyrene 6.0
276
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TABLE 100 (continued)
Constituent Concentration
Nitrosamines and Other N-Compounds
1, 2-Diphenylhydrazine 8.0
Benzidine 3.0
PCB's and Related Compounds
2-Chloronaphthalene 15.0
Pesticides
Isophonone 2.0
277
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TABLE 101. RESULTS OF GC AND GC/MS ANALYSES OF
40-ACRE SEDIMENT SAMPLES
(concentration values in yg/kg dry weight, with no entry
representing concentrations below detected limits)
Sample (40A-ORG-COMP-)
Constituent IB 2B
Halogenated Aliphatics
Dichloromethane (methylene chloride) 47.0 35.0
Trichloromethane (chloroform) 61.0 50.0
Trichloroethene - 0.8
1,1, 2-Trichloroethane 2.0
1, 3-Dichloropropene 2.0
Monocyclic Aromatics
Benzene 28.0 20.0
Toluene 4.0 5.0
Phthalate Esters
Dimethyl phthalate 43.0 46.0
Bis (2-ethylhexyl) phthalate 99.0 60.0
Polycyclic Aromatic Hydrocarbons
Benzo(a)pyrene 26.0 14.0
Acenaphthylene 22.0 50.0
Fluorene - 60.0
Fluoranthene 99.0 55.0
Pyrene - 14.0
Nitrosamines and other N-Compounds
1, 2-Diphenylhydrazine 22.0 46.0
Benzidine 250.0 69.0
Pesticides
Isophorone 13.0 32.0
278
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the effluent from the limited aeration, aeration, and facultative
lagoons (40A-ORG-COMP-3E, 4E, and 5E); and the sludge from the
limited aeration basin (40A-ORG-COMP-6) . Tables 100 and 101 show
the levels of similar organics detected in the settled biologi-
cal sludge from the facultative lagoon (40A-ORG-COMP-7) and the
sediment of the Hurricane Levee Discharge Canal (40A-ORG-COMP-1B
and 2B), respectively.
Discussion of Results--
Comparison of the concentrations of organic constituents in
the 40-Acre lagoon system influent-effluent (Table 99) shows good
assimilation of many groups of wastes, but the concentrations of
some constituents show atypical action. Pentachlorophenol , 4-
nitrophenol, and phenolic compounds are evident in the effluent,
but are not identifiable in the system influent. Chemical or
biochemically induced changes in substrates can occur within the
system, resulting in relatively large differences between mate-
rials in the effluent and that originally introduced.
Based on influent-effluent comparisons, all classes of wastes
show a removal efficiency of 90 percent or greater for the major-
ity of the member compounds.
Nitrobenzene, a monocyclic aromatic, was reduced from an
influent concentration of 58.0 yg/£ to below detection limits
(0.1 yg/£). Previous work reported by Pitter has shown a 98-
percent reduction of the influent concentration when nitroben-
zene was used as the sole carbon source by an acclimated activa-
ted sludge (122). Phthalate esters have been reported to be 98
percent removed after 5 days incubation in a freshwater hydro-
soil (78). The results reported here concur with these observa-
tions. Removal of phthalate esters by the lagoon system was
significant. Fluorene was the only polycyclic aromatic hydro-
carbon not substantially reduced in the system. Removal was 25
percent, a reduction more attributable to dilution of the influ-
ent concentration than to removal. In addition, other organic
compounds removed by the lagoon system included:
• Isophorone, a pesticide (93 percent removal)
• 1,2-Diphenylhydrazine, a nitrosamine (99 percent removed)
• 2-Chloronaphthalene , a PCB-related compound (removed
from 19 yg/a to below detection limits).
Biological treatment performance is difficult to evaluate
without information on both percent oxidation and percent removal
by physicochemical processes but not degraded. A determination
of the organic materials adsorbed intact into the sludge material
(Table 100) gives an indication of the oxidative capability of
the biological system. The number and quantities of organic
279
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compounds identified in the sludge are an indication of the impor-
tance of a biological sludge as a sink for recalcitrant organics.
For example, many more halogenated aliphatics were identified in
the sludge than in the wastewater (Table 99). There are two
explanations for this phenomenon: the halogenated aliphatics
may be intermediate products from the oxidation of other organics,
or the organics were adsorbed prior to the sampling period and
are relatively non-degradabl e in biological systems.
Fluorene was the only compound that did not show a substan-
tial reduction in the influent-effluent comparisons. The fluo-
rene sludge value was 20.0 vg/a , greater than either the influent
or effluent values. This may indicate that the adsorption capa-
city of the biological sludge for fluorene has been exceeded and
that it is not treatable in the concentration detected.
Five compounds (napthalene, acenaphthyl ene , 2 ,4-di ni troto-
luene, phenol, and 4-ni trophenol ) were observed to have higher
concentrations in the biological sludge than in the wastewater.
Acenaphthylene, for example, has a much higher sludge concentra-
tion (70.9 yg/£ ) than wastewater concentration (1.0 to 5.0 yg/£).
This suggests these are biochemically recalcitrant or inert com-
pounds. In addition, the pesticide, 2-chloro naphthalene, has a
sludge concentration (15.0 ug/& ) close to the influent concentra-
tion (19.0 vg/i ) .
Conversely, low concentrations of other organic constituents
in the sludge and effluent indicate oxidation of these materials.
Organics in this category are: bis- (2-chl oroethoxy) methane,
nitrobenzene, dibutyl phthalate, acenaphthene , phenanthrene , 1,2
diphenyl hydrazine , and benzidine.
Table 101 presents the results of the analyses of the sedi-
ments from the Hurricane Levee Discharge Canal; 40A-ORG-COMP-1 B
was taken 90 m (300 ft) from the 40-Acre effluent point, and 40A-
ORG-COMP-2B was taken at the effluent point. These data indicate
that the sediment of the receiving waters is a sink for organic
materials. Higher organic concentrations were found in the sedi-
ment samples than in the biological sludge sample. No ethers or
phenol and cresol compounds were identified in the sediments.
Two mechanisms are responsible for the partitioning of orga-
nics into the sediment: the affinity of clay particles (the pre-
dominate soil constituent found in the sediments) for organic
molecules, or the salting out of organic molecules in the brack-
ish water of the Hurricane Levee Discharge Canal.
Biological Analyses Results--
Wet mount, gram-stain, and identification summary — The anaer-
obe lagoon (40A-BIO-GRAB-1 IS ) contained gram-negative, feebly
motile rods, mostly in pairs (Pseudomonas sp); many gram-negative,
280
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curved (vibroid) .forms (Comamonas sp); and many large, gram-posi-
tive yeast cells with budding. In addition, an unusual unidenti-
fied bacteria, gram-negative and nonmotile, was found in the
anaerobic lagoon. This bacteria was curved to such an extent
that the ends of the microbe almost met. A photosynthetic bac-
teria belonging to the family Thiohodaceae was also identified
in the anaerobic lagoon.
The flora found in the aeration basins and active faculta-
tive lagoon contained predominately gram-negative microbes. These
included Pseudomonas, Caulobacter, Arthrobacter, and a chromo-
bacteria. Other microbes found in the samples include Flavobac-
terium, Enterobacter, and several yeasts.
The limited aeration basin contained the curved bacteria
found in the anaerobic lagoon in addition to those microbes iden-
tified in the aeration basin biological sludge. The population
of the inactive facultative lagoon (40A-BIO-GRAB-5S) was too
sparse to characterize under oi1-immersion .
Most Probable Number (MPN) Results--Co1iforms per 100 mi
sample were:
40A-BIO-GRAB-1S : No coliforms detected
40A-BIO-GRAB-2S: No coliforms detected
40A-BIO-GRAB-3S: MPN: 2.0 x 101 Confidence:
0.43-9.4 x IQl
40A-BIO-GRAB-4S : No coliforms detected
40A-BIO-GRAB-5S: No coliforms detected
Subcultures of eosin methylene blue agar of 40A-BIO-GRAB-3S yield-
ed typical Enterobacter sp. colonies.
Plate Count Resu1ts--(in terms of viable microbes per 1.0
ma sample):
40A-BIO-GRAB-1S: 3.3 x 1 O7
40A-BIO-GRAB-2S: 8.2 x 1 O7
40A-BIO-GRAB-3S: 2.0 x 106
40A-BIO-GRAB-4S: 7.0 x 107
40A-BIO-GRAB-5S: 3.8 x 106
Discussion of re suits--The microorganisms identified in the
40-Acre biological sludge are similar in type to the microbes
found in domestic wastewater biological treatment. Dominant
types of microorganisms isolated from domestic treatment plants
include Achromobacter, Alcaligenes, Comomonas, Flavobacteriurn,
281
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Pseudomonas, Enterobacteriaceae, Thiobaci11 us, and Zoogloea (23,
57). This similarity of microbial type is most apparent in the
aeration basin biological sludge microbes. Microbes identified
in this aeration basin sludge include Pseudomonas sp. , Comamonas
sp. . Enterobacter sp., Flavobacteriurn, and Zoogloea.
Previous studies have shown that microbes acclimate to a var<
iety of wastes (122). Thus, the identification of similar micro-
bial types between industrial and domestic wastewater treatment
is not surprising.
Pseudomonas, a facultative anaerobe, was identified in the
anaerobic lagoon sludge. However, the Pseudomonas isolated were
feebly motile and not as vigorously motile as the Pseudomonas
isolated from the aeration basins. In addition, large gram-posi-
tive yeast cells with budding were identified in the anaerobic
lagoon sludge. Yeasts have been noted for the ability to meta-
bolize certain organic substrates (153).
Phostosynthetic bacteria belonging to the family Thiorhoda-
ceae were identified in the anaerobic lagoon. The strong, pink
color of the anaerobic lagoon sample suggests a large population
of the purple sulfur Thiorhodaceae: Thiopedia rosea. Theopedia
rosea has been indicated as being responsible for reducing odor
emissions from anaerobic lagoons (30). This microaerophi1ic
bacteria uses hydrogen sulfide as the electron donor in photo-
synthesis and produces some type of oxidized sulfur compound as
the end product. Thiopedia rosea has been isolated from West
Coast anaerobic lagoons treating wastes from a large oil refinery
and an animal fat rendering plant (30).
Washburn Tunnel Facility
The Washburn Tunnel Facility, a large high-rate activated
sludge system, treats a flow of approximately 1.7 x 105 m3/day
(45.0 MGD). The treatment process includes barscreening, grit
removal, primary clarification, nutrient addition, pH control,
activated sludge, and secondary clarification. Currently, sludge
generated is dewatered in filter presses or centrifuges and
barged to an off-site landfill. Plans call for incineration in
the future.
During the sampling period Washburn Tunnel treated seven
industrial waste streams, A through 6, and discharges to the
Houston Ship Channel. Section IV gives a more detailed site
description.
For this study, Washburn Tunnel was sampled for four days,
December 11 to 15, 1977. Characterization of the Washburn Tun-
nel wastewater and effluent loading values in kg/day (Ib/day)
for the sampling is presented in Table 102.
282
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TABLE 100. CHARACTERIZATION OF WASHBURN TUNNEL WASTEWATER AND
EFFLUENT LOADING IN KG/DAY (LB/DAY) FOR SAMPLING PERIOD
Wastewater
Characteristic
Wastewater
Loading
Effluent
Loading
Percent
Removal
Flow x 105 m3/day (M6D)
TOC
COD
BOD
TSS
NH3-N
Phenol
1.7 (450) 1.6 (42.0)
32,251 (70,952.2)21,646 (47,621.2) 33
266,905 (587,191) 76,066 (167,345.2) 72
49,511 (108,924) 6,835 (15,037)
146,448 (322,186) 19,144 (42,117)
1,250 (2,750) 86.37(190)
144.9 (318.8)
11.59(25.5)
86
87
93
92
283
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Sampling Sites and Frequency--
The sampling program at Washburn Tunnel was designed to
identify the fate of organic compounds in the treatment process
and the active microbial populations present in the system.
Figure 54 shows the sites within the Washburn Tunnel Facil-
ity selected for sampling. Table 103 lists the organic and bio-
logical samples taken at the site, their location and sample
identification designation.
Seven waste streams are treated at the facility. Five enter
at influent point I (influents A through E) and two at Manhole
#4 (influents F and G), as shown in Figure 54. Influents A through
E (WT-ORG-COMP-I1) were composite sampled at a point past the bar
screen in the grit chamber. The primary clarifier effluent (WT-
ORG-COMP-I2) was composite sampled at the T-ll wet well. Because
wastewater flow into the two primary clarifiers was equal, sam-
pling of only one clarifier effluent was considered adequate- The
effluents from the primary clarifiers combine with influents F
and G at Manhole #4 before they enter the aeration basins (Figure
54). A composite sample was taken at the cooling tower wet well
(WT-ORG-COMP-AI).
The final effluent sample (WT-ORG-COMP-E) was obtained from
a GCWDA refrigerated composite sampler. This sampler collects
approximately 8 to 10 effluent samples/day. Approximately 1.0 a
aliquots were taken from this final effluent sample and trans-
ferred to a single 4-£ bottle each day for the duration of the
sampling period.
Grab samples of sludge were taken from the final clarifiers
(WT-ORG-COMP-S16/17/27). The grab samples were adequate for
obtaining samples from the aeration basins; however, problems were
encountered in grab sampling at the final clarifiers. Determi-
nation of the sludge blanket level in the final clarifiers was
both difficult and time-consuming. The use of submersible pumps
(8 £/min) to obtain the l-£ sample solved the problem. A quick
determination of the sludge blanket level could be made with the
pumps, and rapid sampling was, therefore, possible.
Biological samples for microbial population studies were
taken from four of the final clarifiers (T-16, T-17,«27A, and
27B) and the three aeration basins (T-19, T-20, and T-21). Both
the grab sampler and the submersible pumps were used to obtain
these samples.
Sediment samples for organic analyses were grabbed from the
Houston Ship Channel using the La Motte Dredge. One sample was
taken at the Washburn Tunnel effluent outfall (WT-ORG-GRAB-SED2)
and another 180 m (600 ft) upstream from the outfall (WT-ORG-GRAB-
SED1). Figure 54 shows the approximate location of these sampling
stations.
284
-------
ro
oo
en
1
2
3
4
SAMPLE LEGEND
COMPOSITE FOR ORGANIC ANALYSIS
GRAB FOR ORGANIC ANALYSIS
GRAB FOR BIOLOGICAL ANALYSIS
SEDIMENT GRAB FOR ORGANIC ANALYSIS
HOUSTON SHIP CHANNEL
1. BAM SCREEN
2. GRIT CHAMBER
3. PRIMARY CLARIFIER
4. NEUTRALIZATION
5. NUTRIENT ADDITION
6. COOLING TOWER
7a. AERATION BASIN (OLD)
7b. AERATION SASIN (NEW)
8a. FINAL CLARIFIERS (OLD)
8b.FINAL CLARIFIERS (NEW)
9. FILTER PRESS BLDG.
10. INCINERATOR
11. BARGE
12. HOLDING BASINS
13. LAB & OFFICE BLDG.
INFLUENTS A-E
Figure 54. Washburn Tunnel facility layout and sampling sites.
-------
TABLE 103. WASHBURN TUNNEL FACILITY ORGANIC AND BIOLOGICAL
SAMPLE LOCATIONS AND IDENTIFICATION DESIGNATIONS
A. Samples for Organic Analysis
LOCATION
Influent for all wastes except Influent -F&6
Primary Effluent
Influent to all aeration basins (after cooling tower )
Sludge from basins T-16, T-17, and 27
A to D
Plant effluent
Sediment, upstream of outfall
Sediment, at outfall
B. Samples for Biological Analysis
LOCATION
Aeration basin T-19
Aeration basin T-20
Aeration basin T-21
Sludge from T-16 and T-17
DESIGNATION
WT-ORG*-COMP*-I1
WT-ORG-COMP-I2
WT-ORG-COMP-AI
WT-ORG-COMP-S16/
17/27
WT-ORG-COMP-E
WT-ORG-GRAB*-SED1
WT-ORG-GRAB-SED2
DESIGNATION
WT-BIO*-COMP-T-19
WT-BIO-COMP-T20
WT-BIO-COMP-T21
WT-BIO-GRAB-S2
Notes.
ORG - organic analysis samples.
COMP - composite samples taken according 'to Sampling Methods.
BIO - biological samples for microbial analysis.
GRAB - grab samples taken according to Sampling Methods.
286
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Chemical Analyses Results--
The results of the organic analyses of the samples taken at
the Washburn Tunnel Facility are presented in Tables 104 through
106. The explanation of the sample designations used in these
tables is given in Table 103 and shown in Figure 54.
Table 104 shows the organic chemical constituents present in
the influent sources to the Washburn Tunnel, WT-ORG-COMP-I1 , 12,
and AI, and the effluent from the facility, WT-ORG-COMP-E . Tables
105 and 106 show the levels of similar organics present in the
biological sludge from the final clarifiers (WT-ORG-COMP-S16/17/27)
and the sediment samples obtained from the Houston Ship Channel
(WT-ORG-GRAB-SED1 and SED2), respectively.
Discussion of Results--
Comparison of the concentrations of organic constituents in
the Washburn Tunnel Facility influent-effluent (Table 104) shows
assimilation of many groups of wastes, but not to the same degree
as exhibited by the 40-Acre lagoon system. Removal, for the
majority of the wastes, is approximately 50 percent, whereas the
40-Acre efficiency was 90 percent or greater. This suggests that
retention time plays an important role in assimilation of hazar-
dous organic materials. The retention time in activated sludge
systems may not be adequate for biosorption. The short retention
time in an activated sludge system may cause microbes to concen-
trate on the easier-to-degrade organics.
Groups of organics showing substantially greater than 50 per-
cent removal (based on influent-effluent comparisons) were the
halogenated aliphatics, ethers, and monocyclic aromatics. The 2,
4-di ni trotol uene was reduced from 390.0 yg/ a to below detection
limits, and 4-bromophenyl phenyl ether was reduced from 258.0 to
0.2
Phenol showed only a 26-percent reduction and 1, 2-diphenyl-
hydrazine, a nitrosamine, a 28-percent reduction. Benzidine,
also a nitrosamine, showed no influent-effluent reduction. Ben-
zidine was reduced 75 percent in the 40-Acre lagoon system. Flu-
orene, which was reduced only 25 percent in the 40-Acre system,
was reduced by 65 percent in the Washburn Tunnel system.
Historically, phenol has been removed 98 percent in the Wash-
burn Tunnel treatment system (Table 75). The discrepancy between
the removal efficiencies could be due to the differences in the
phenol removal averaged for a year's sampling, whereas Table 104
reports removals for only a four-day sampl i ng period .
The analysis for the Washburn Tunnel sludge (Table 105) shows
a similar abundance of organic compounds as in the 40-Acre sludge.
Certain of these compounds were found in high concentrations.
Halogenated aliphatics (1, 2-dichl oroethene , 1,1, 1 -tri chl oroe-
thane, and tetrachl oromethane) were found in the 2 to 5 mg/i range.
287
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TABLE 104. RESULTS OF GC ANALYSIS OF COMBINED EXTRACTS OF
BASE/NEUTRAL AND ACID FRACTIONS ISOLATED FOR
WASHBURN TUNNEL SAMPLES
(concentration values in yg/1, with no entry representing
concentrations below detection limits)
Sample (WT-ORG-COMP)
Constituent
Halogenated Aliphatics
Hexachlorocyclopentadiene
Bis (2-chloroethoxy) methane
Ethers
Bis (2-chloroisopropyl ) ether
4-Bromophenyl phenyl ether
Bis (2-chloroethyl) ether
Monocyclic Aromatics
1, 2, 4-Trichlorobenzene
2, 4-Dinitrotoluene
Phenols and Cresols
2-Chlorophenol
2, 4-Dimethyl phenol
2-Nitrophenol
Phenol
p-chloro-m-cresol
2, 4, 6-Trichlorophenol
Dichlorophenol
Phthalate Esters
Dimethyl phthalate
Diethyl phthalate
Bis (2-ethylhexyl) phthalate
di-n-butyl phthalate
Butyl benzyl phthalate
Polycyclic Aromatic Hydrocarbons
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benzo(a) pyrene
Benzo(a) anthracene
Benzo(b) fluoranthrene
11 12
29.0
358.0
19.0
0.9
0.1
43.0
68.0
4.0
4.0
1.5 0.6
1.0
2.0
30.0
1.2
0.4
0.6 1.0
0.9
2.0
3.0
17.0
76.0
5.0
AI
113.0
134.0
0.2
18.0
28.0
390.0
0.9
15.0
9.0
8.0
4.0
2.0
6.0
2.0
*4.0
1.0
1.0
280.0
1.0
2.0
9.0
E
2.0
0.2
0.6
32.0
17.0
1.0
3.0
0.9
2.0
0.2
0.5
98.0
1.0
1.0
5.0
288
-------
TABLE 104 (continued)
Sample (WT-ORG-COMP-)
Constituent
II
12
AI
Nitrosamines and Other N-Compounds
1, 2-Diphenylhydrazine
Benzidine
RGB's and Related Compounds
2-Chloronaphthalene
Pesticides
Isophorone
1.6
247.0 341.0 244.0
4.0 4.0 4.0
2.0
0.2
1.0 0.2
289
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TABLE 105. RESULTS OF GC/MS ANALYSIS OF WASHBURN TUNNEL
SLUDGE SAMPLES WT-ORG-COMP-S16/17/27
(concentration values in yg/1)
Constituent Concentration
Halogenated Aliphatics
1, 2-Dichloroethene 2,900.0
1, 3-Dichloro-l-propene (trans) 145.0
1, 3-Dichloro-l-propene (crs) 31.0
Trichloroethene 18.0
1,1, 1-Trichloroethane 5,490.0
Tetrachloromethane (carbon 2,375.0
tetrachloride)
Monocyclic Aromatics
Benzene 1,233.0
Toluene 233.0
2, 4-Dintrotoluene 2.0
2, 6-Dintrotoluene 0.5
Phenols and Cresols
2, 4, 6-Trichlorophenol
2, 4-Dimethylphenol 0.9
2-Chlorophenol 0.5
Phenol 0.5
p-chloro-m-cresol 1.0
Phthalate Esters
Diethyl phthalate 0.5
Dioctyl phthalate 20.0
Polycyclic Aromatic Hydrocarbons
Acenaphthylene 0.5
Acenaphthene 0.5
Fluoranthene 1.0
Nitrosamines and Other N-Compounds
Benzidine 1.0
PCB's and Related Compounds
2-Chloronaphthalene 0.5
Pesticides
Isophorone 1.0
290
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TABLE 106. RESULTS OF GC AND GC/MS ANALYSES OF
WASHBURN TUNNEL SEDIMENT SAMPLE
(concentration values in ng/Kg dry weight, with no entry representing
concentrations below detection limits)
Sample (WT-ORG-GRAB-)
Constituent
Halogenated Aliphatics
Dichloromethane
1, 1-Dichloroethene
1, 2-Dichloroethene
Trichloromethane (chloroform)
1, 3-Dichloro-l-propene
Trichloroethene
1,1, 2-Trichloroethane
1,1, 22-Tetrachloroethane
Hexachlorocyclopentadiene
Ethers
4-Bromophenyl phenyl ether
Bis (2-chloroethyl) ether
Monocyclic Aromatics
Benzene
Toluene
Nitrobenzene
2, 4-Dinitrotoluene
Phenols and Cresols
2-Nitrophenol
2-Chlorophenol
Phenol
p-chloro-m-cresol
2, 4, 6-Trichlorophenol
Phthalate Esters
Dimethyl phthalate
Di ethyl phthalate
Di-n-butyl phthalate
Polycyclic Aromatic Hydrocarbons
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Benzo(a) pyrene
SED1
959.0
8.0
3.0
310.0
1.0
2.0
2.0
1.0
-
1,056.0
1,940.0
63.0
4.0
65.0
1,379.0
86.0
56.0
345.0
1,250.0
560.0
-
267.0
323.0
103.0
474.0
647.0
1,293.0
-
496.0
216.0
SED2
1,964.0
0.2
_
258.0
-
0.9
1.4
2.0
106.0
69.0
-
15.0
-
-
46.0
-
-
115.0
-
115.0
106.0
138.0
—
59.0
37.0
115.0
321.0
92.0
298.0
46.0
291
-------
TABLE 106 (continued)
Constituent
Sample (WT-ORG-GRAB-)
SED1
SED2
Nitrosamines and Other N-Compounds
Benzidine
1, 2-Diphenylhydrazine
Pesticides
Isophorone
517.0
2,112.0
483.0
505.0
367.0
206.0
292
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Monocyclic aromatics benzene and toluene were 1,233.0 and 233.0
ug/£, respectively. None of these organics were identified in
the Washburn Tunnel influent-effluent. The high concentrations
of these organics in the sludge suggests that they are recalci-
trant compounds.
The remaining organics in the sludge were all below 50 g/a
in concentration. The 2, 4-dinitrotoluene was reduced from 390.0
yg/£ in the influent and was below the detection limits in the
effluent. The sludge concentration was 2.0 yg/£, suggest!ng bio-
oxidation of 2, 4-dinitrotoluene or the removal of the nitro
groups and conversion of the compound to toluene (233.0 yg/2. in
the sludge). This is also true for the ethers. Ethers are rela-
tively volatile compounds and may be air-stripped in the aera-
tion basis. None of the ethers identified in the wastewater were
found in the sludge.
The fluorene concentration was lowered by 65 percent in the
treatment system, from 280.0 to 98.0 yg/£. Fluorene was not
identified in the sludge, a contradiction to the fluorene con-
centration in the 40-Acre sludge, where fluorene was a major
constituent.
The sediment grabbed from the Houston Ship Channel at and
near the Washburn Tunnel outfall was a black, viscous material,
with a strong smell of oil. The Houston Ship Channel carries a
high volume of ship traffic and has a number of water-using indus-
tries located along its shores. Consequently, it is impossible
to confirm the origin of the organics identified in the sediments.
This is apparent when the upstream sediment concentrations are
compared to the outfall sediment concentrations (Table 106). The
sample grabbed upstream of the Washburn Tunnel outfall, WT-ORG-
GRAB-SED1, has a greater concentration than the outfall sample.
Therefore, it is not possible to attribute any of the conditions
observed in the receiving environment exclusively to the Washburn
Tunnel operation.
The data illustrate the affinity of clay sediments for orga-
nics. Many organic compounds were identified in the sediment,
with concentrations in the mg/£ range.
Biological Analyses Results--
Wet mount, gram-stain, and identification summary--F1ora
was qualitatively uniform throughout. Gram-negative organisms
were dominant, comprising over 95 percent of the cells observed.
The gram-positive forms observed were primarily cocci with an
occasional yeast. A few unicellular algae and debris, possible
fungal hyphae, were also identified.
The predominant organisms seemed to be gram-negative, vig-
orously motile rods about 1.5 x 0.5 micra, mostly single but some
293
-------
in pairs (Pseudomonas sp.). Stalked, gram-negative bacteria
(Caulobacter sp.) were very common and were attached to floes
of debris and bacteria. Other bacteria found included a gram-
negative, short, plump, rod staining uniformly and densely,
mostly single but some in pairs and rare chains (Chromobacteria,
red-orange pigmented), and a gram-negative bacterial filament
of about 1 x 40 to 80 micra in length (Arthrobacter sp.) .
The WT-BIO-COMP-T20 sample yielded Thiobacillus ferrooxi-
dans, although all samples contained thiosulfate-oxidizing
autotrophs and possibly ammonia-oxidizing bacteria.
Other common microbes found in the samples included Flavo-
bacterium, Enterobacter, and several yeasts (not characterized).
Most probable number (MPN) results--Coliforms per 100 ma
sample were:
,5
WT-BIO-COMP-T19
WT-BIO-COMP-T20
WT-BIO-COMP-T21
WT-BIO-GRAB-S2:
MPN:
MPN:
MPN:
MPN:
2.5 x
6.0 x
2.5 x
1 .3 x
10 Confidence:
4
10 Confidence:
105 Confidence:
10 Confidence:
0.38-16.0 x 10*
0.91-40.0 x 10Z
0.38-16.0 x
7.0 -86.0 x
10
Subcultures of eosin methylene blue agar revealed colonies typi-
cal of Enterobacter aerogenes. No Escherichia coli was detected.
Plate count results — tin terms of viable microbes per 1.0 ma):
WT-BIO-COMP-T19:
WT-BIO-COMP-T20:
WT-BIO-COMP-T21 :
WT-BIO-GRAB-S2:
1 .35 x 10'
8.1
5.0
x 10'
x 10'
6.2 x 10'
Discussion of resul ts_--The microflora identified in the
Washburn Tunnel biological sludge are comparable to the micro-
flora common to domestic activated sludge sewage treatment. The
exception, Escherichia coli . a microbe ubiquitous in domestic
sewage, was not isolated from the sludge. The absence of an
enteric bacteria is not unusual; Washburn Tunnel handles no
sanitary wastes.
Pseudomonas, the predominate microbe isolated from the
sludge, has been noted previously as being the dominant organism
in treating carbohydrate-rich wastes (57). The predominance
of Pseudomonas in the Washburn Tunnel activated sludge is an
indication of the ability to acclimate to various organic
substrates, both domestic and industrial.
294
-------
A major waste source (60 to 70 percent) to the Washburn
Tunnel is a kraft paper mill effluent. A recent study has indi-
cated the association of coliform bacteria, specifically Kleb-
siella, of nonfecal origin with pulp mill wastes (83). This
study found MPN results of 105 cells per 100 m£ for coliform
bacteria. Selective media growth tests were performed on iso-
lates from the MPN tests with eosin methylene blue agar. These
tests revealed colonies typical of Enterobacter aerogenes. The
results of the two studies, the association of high numbers of
coliform bacteria with paper manufacturing effluent, suggest
coliform bacteria assimilation of wood pulp wastes. Yeasts,
which were also isolated from the sludge, have been noted for
removal of resins from kraft mill effluents (153).
The iron-oxidizing bacteria, Thiobaci11 us ferroxidans , was
isolated from the biological sludge. In addition, all samples
contained thiosulfate-oxidizing autotrophs and possibly ammonia-
oxidizing bacteria.
ECO Deep Shaft Facility
The Deep Shaft treatment plant in Paris, Ontario, Canada is
a pilot system. It treats a portion of the wastewater received
at a conventional extended aeration wastewater treatment plant
operated by the Ontario Ministry of the Environment. The Deep
Shaft Facility is capable of treating 473 m3/day (0.12 MGD) of
difficult-to-treat industrial/domestic blends. The industrial
waste components come from 14 sources, the major source a tex-
tile plant. Total retention time is 30 min.
The Deep Shaft Facility, a secondary biological process,
uses a totally enclosed subsurface aeration shaft. Fluid pres-
sure with depth creates increased oxygen solubility and enhan-
ces oxygen transfer efficiency.
Deep Shaft was sampled for five days March 13 to 17, 1978.
During the sampling period, the wastewater treatment scheme con-
sisted of bar screening, comminutor, acid neutralization, deep
shaft biooxidation, air flotation, and discharge to the main
plant. Characteristics of the influent and effluent loading
values for conventional parameters during the sampling period
are presented in Table 107.
Sampling Sites and Frequency--
Figure 55 shows the sites selected for sampling at the Deep
Shaft Facility. Table 108 presents a list of the organic and
biological samples taken, their location, and the sample identi-
fication designation. The following discussion explains the
selection of the sampling sites.
Samples for organic analysis were taken at various points
in the system. The influent sample (DS-ORG-COMP-I) was obtained
295
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TABLE 107. CHARACTERIZATION OF THE DEEP SHAFT WASTEWATER AND
EFFLUENT LOADING IN KG/DAY (LB/DAY) FOR THE SAMPLING PERIOD
Wastewater Wastewater Effluent Percent
Characteristic Loading Loading Removal
Flow x 102 m3/day (MGD) 4.5 (0.12) 4.5 (0.12)
Total BOD5 82 (181) 15 (33) 82
Soluble BOD5 33 (73) 6 (13) 82
COD5 403 (888) 90 (198) 78
SS 140 -(309) 27 (60) 81
296
-------
SAMPLE LEGEND
1 COMPOSITE FOR ORGANIC ANALYSIS
2 GRAB FOR ORGANIC ANALYSIS
3 GRAB FOR BIOLOGICAL ANALYSIS
COMMINUTOR
RECYCLE SLUDGE
RAW
SEWAGE
DOWNCOMER—"^
WASTE
SLUDGE
TO RECEIVING
WATERS
Figure 55. Paris Deep Shaft Facility.
-------
TABLE 108. DEEP SHAFT FACILITY ORGANIC AND BIOLOGICAL
SAMPLE LOCATIONS AND IDENTIFICATION DESIGNATIONS
A. Samples for Organic Analysis
LOCATION
Influent to shaft
Effluent from flotation tank
Influent to shaft
Effluent from shaft
Waste mixed liquor
B. Samples for Biological Analysis
LOCATION
Effluent from shaft
Bottom sludge from air flotation tank
Floated sludge from air flotation tank
DESIGNATION
DS-ORG*-COMP -I
DS-ORG-COMP-EF
DS-ORG-GRAB-I
DS-ORG-GRAB-SEF
DS-ORG-COMP-WS
DESIGNATION
DS-BIO*-GRAB*-SEF
1-DS-BIO-GRAB-WS
2-DS-BIO-GRAB-WS
*Notes.
ORG - organic analysis samples.
COMP - composite samples taken according to Sampling Methods,
BIO - biological samples for microbial analysis.
GRAB - grab samples taken according to Sampling Methods.
298
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from a refrigerated composite sampler (Sirco). The effluent
sample (DS-ORG-COMP-E) was obtained with a composite sampling
set-up developed for this study. The composite sampler was also
used to obtain the waste sludge sample (DS-ORG-COMP-WS) from the
head tank of the shaft. During the sampling period, 1-i ali-
quots were taken from 4-£ composite samplers and composited into
single 4-£ bottles daily.
Grab samples for organic analysis were taken from the influ-
ent (DS-ORG-GRAB-I) and shaft effluent (DS-ORG-COMP-SEF). The
influent sample was obtained from a draw-off spigot on the influ-
ent pipe from the surge tank, the shaft effluent sample from the
spigot on the shaft effluent pipe from the riser to the flota-
tion tank.
Biological samples for the microbial population study were
grabbed from the shaft effluent (DS-BIO-GRAB-SEF) , the air flo-
tation tank bottom sludge (1-DS-BIO-GRAB-WS) , and the air flo-
tation tank-floated sludge blanket (2-DS-BIO-GRAB-WS). The shaft
effluent sample was drawn from a spigot on the shaft effluent
pipe from the riser to the flotation tank.
Chemical Analyses Results--
The results for the organic analyses of the Deep Shaft
Facility are presented in Tables 109 and 110. An explanation
of sample designations used in these tables is given in Table
108.
Table 109 shows the organic chemical constituents detected
by composite sampling of the shaft influent (DS-ORG-COMP-I),
the effluent from the entire system (DS-ORG-COMP-EF) , and the
waste mix liquor from the shaft (DS-ORG-COMP-WS). Table 110
shows the levels of similar organics detected in the grab sam-
ples taken from the shaft influent (DS-ORG-GRAB-I) and the efflu-
ent from the shaft (mixed liquor) (DS-ORG-GRAB-SEF) during a
peak dye discharge.
Sludge at this Deep Shaft pilot plant is wasted from both
the floated and bottom sludge from the air flotation tank. There-
fore, to obtain a representative sampling of total sludge, a sam-
ple of the mixed liquor was taken from the shaft head tank. The
percent solids by weight of this sample was 0.56 percent.
Discussion of results—Comparison of influent-effluent and
waste sludge concentration values (Table 109) shows a variety
of organics in each sample. Influent chloroform concentration
is 22.0 mg/£, the sludge concentration is 1.9 mg/2,, and the efflu
ent concentration is below detection limits. Carbon tetrachlor-
ide influent concentration is 2.2 mg/£, and the effluent and
waste sludge concentrations are below detection limits. Volati-
lization of these organics may be a major removal pathway. Chlo-
roform inhibits bacterial cell multiplication at concentrations
299
-------
TABLE 109. RESULTS OF GC AND GC/MS ANALYSES OF
DEEP SHAFT COMPOSITE SAMPLES
(concentration values in yg/1, with no entry representing
concentrations below detection limits)
Constituent
Halogenated Aliphatics
Dichloromethane
Trichloromethane (chloroform)
Tetrachloromethane (carbon tet. )
1,1, 2-Trichloroethane
Tetrachl oroethene
1, 1, 2, 2-Tetrachloroethane
Trichl oroethene
1, 3-Dichloro-l-propene
Monocyclic Aromatics
Benzene
Toluene
1, 2, 4-Trichlorobenzene
Chlorobenzene
2, 4-Dinitrotoluene
2, 6-Dinitrotoluene
Nitrobenzene
Phenols and Cresols
Phenol
2, 4-Dimethylphenol
2-Chlorophenol
2, 4, 6-Trichlorophenol
Pentachlorophenol
Phthalate Esters
Dimethyl phthalate
Dioctyl phthalate
Polycyclic Aromatic Hydrocarbons
Acenaphthene
Anthracene
Chrysene
Phenanthacene
Benzo(a) pyrene
Nitrosamines
Benzidine
Sample
I
-
22,000.0
2,185.0
11.0
5.0
8.0
18.0
-
336.0
30.0
5.0
-
-
-
-
18.0
-
-
-
-
70.0
1,000.0 5
180.0
-
-
_
-
_
(DS-ORG-COMP-)
EF
-
1,
-
-
-
-
-
-
_
-
-
100.0
100.0
200.0
-
_
-
100.0
1,
1,
200.0
,000.0 2,
_
500.0 .
100.0
2,
1,
200.0
WS
20.0
938.0
-
-
1.0
3.0
1.0
235.0
14.0
5.0
34.0
-
500.0
700.0
100.0
15.0
150.0
-
000.0
000.0
_
010.0
41.0
-
-
000.0
000.0
_
300
-------
TABLE 109 (continued)
Sample (DS-ORG-COMP-)
Constituent
EF
WS
Pesticides
Isophorone
Chlordane*
ODD*
7.0
0.2
0.1
Alkyl stannane
Monochloroalkyl stannane
Hexadecanoic acid (Palmic acid)
< 10.0
< 10.0
>100.0
*BothGC-ECD assignments unconfirmable by GC/MS due to low levels,
Due to banned status of chlordane and DDD's precursor (DDT) in
Canada, assignments are doubtful.
301
-------
TABLE 110. RESULTS OF CG AND GC/MS ANALYSES OF
DEEP SHAFT GRAB SAMPLES
(concentration values in yg/1, with no entry representing
concentrations below detection limits)
Sample (DS-ORG-GRAB-)
Constituent I SEF
Halogenated Aliphatics
Dichloromethane - 13.0
Trichloromethane (chloroform) - 2,309.0
1,1, 2-Trichloroethane - 1.0
1, 3-Dichloro-l-propene (trans) - 66.0
1, 3-Dichloro-l-propene (cis) - 4.0
1, 1-Dichloroethene - 3.0
Monocyclic Aromatics
Benzene - 193.0
Toluene - 26.0
Trichlorobenzenes - 1,000.0
Chlorobenzene 10.0
Nitrobenzene - 300.0
Phenols and Cresols
Phenol 1,000.0 1,500.0
2-Chlorophenol 10.0
Dinitrophenol - 100.0
2, 4, 6-Trichlorophenol - 500.0
p-chlorocresol - 1,000.0
Pentachlorophenol - 1,000.0
Phthalate Esters
Dimethyl phthalate - 1,000.0
Diethyl phthalate - 1,000.0
Dioctyl phthalate 2,000.0 10,000.0
Polycyclic Aromatic Hydrocarbons
Acenaphthene - 100.0
Dibenzo(g,h,i) perylene 50.0
Benzo fluoranthene 700.00
Benzo(a) pyrene 200.0 4,000.0
*
Pesticides
Chlordane - 100.0
302
-------
greater than 125 mg/x, and carbon tetrachloride inhibits it at
concentrations greater than 30 mg/£ (163). In addition, the
alkyl stannanes identified are newly developed compounds that
are effective biostats and are added to surface paints to res-
trict fungal or mold growth. The use of these chemicals in an
aqueous medium is banned in the United States, but their status
in Canada is now known. It is also not known if the concentra-
tions determined in the waste sludge (<10.0 yg/£) are biocidal.
The chloroform, carbon tetrachloride, and stannanes may be
limiting factors to the assimilative capacities of the Deep Shaft
The assimilation of BOD and other wastewater pollutant parameters
by the Deep Shaft may improve when the influent concentrations
of these chemicals is limited.
Biological Analyses Results--
Wet mount, gram-stain, and identification summary—The shaft
eff1uent(DS-BIO-GRAB-SEF)contained mainly gram-negative, vigor-
ous, motile rods and cocco-baci11 us. The most common organism
found was a small, motile, gram-negative rod that occurred singly
and in pairs (Pseudomonas sp _.) . Stalked gram-negative bacteria
(Caulobacter spT)were found attached to floes, which were com-
posed of gram-negative material. Very small gram-negative cocci
(Micrococcus sp.) were found singly or in pairs. Occasional
large, blunt, gram-positive rods (Baci 1 1 us sp.) were found asso-
ciated with the floes.
The air flotation tank floated sludge (2-DS-BIO-GRAB-WS)
contained mostly small, motile, gram-negative rods. A few gram-
positive rods and cocci were associated with the gram-negative
floe-bacteria complexes. The flotation tank bottom sludge (1-DS-
BIO-GRAB-WS) contained small motile gram-negative rods, gram-
negative coccibaci11i , and larger, gram-negative, blunt, dense,
staining bacilli (D e s u 1 f o v i b r i o desulfuricans and/or T h i o b a c i1 -
1 us sp .) .
Other common microbes found in the samples were Escherichia
col i , Enterobacter aerogenes , Pseudomonas f1uorescans , Flavo-
bacterium sp. , chromobacteria (red-orange-pink), sulfur oxidizers
(ThiobacTl 1 us sp.) , yeasts, and a streptomycete .
Most probable number (MPN) resul ts--Co1iform per 100 mi
mp
DS
1-
2-
le
-B
DS
DS
:
10-
-BI
-BI
GRAB-S
0-GRAB
0-GRAB
EF:
-WS:
-WS:
MPN:
MPN :
MPN:
1
4
2
.5
.5
.5
X
X
X
1
1
1
0
0
0
6
6
5
Confidence
Confidence
Confi dence
3.2-70.0 x 10
1 .0-12.0 x 10
0.5-12.0 x 10
303
-------
Plate count results--Microbes per 1.0 ma sample:
DS-BIO-GRAB-SEF: 1.2 x 109
1-DS-BIO-GRAB-WS: 5.9 x 109
2-DS-BIO-6RAB-WS: 8.5 x 1O8 .
Discussion of results—The Paris Deep Shaft Facility treats
a 70:30 industrial/domestic wastewater blend; the biological seed
originates at the adjacent municipal wastewater treatment facil-
ity. Consequently, the flora at the Deep Shaft Facility is simi-
lar to that of a municipal biological sludge.
A Pseudomonas bacteria was the most common organism found in
the effluent. This compares to the predominance of Pseudomonas
in the activated sludge and lagoon system biological sludges. In
addition, other organisms included enteric bacteria, a fungi,
yeasts, and sulfur oxidizing bacteria.
Biological analyses were performed on the air flotation tank
floated sludge and the bottom return sludge to compare the flora
associated with each sludge. The floated sludge contained mainly
Pseudomonas associated with floe-bacteria complexes. The bottom
return sludge contained Pseudomonas, Micrococcus, and Bacillus
bacteria, and a gram-negative, dense-staining bacilli identified
as Desulfovi brio desulfuricans or a Thiobaci11 us . Both bacteria
are sulfur-oxidizing bacteria. These normally autotrophic orga-
nisms have been known to metabolize organic compounds (109).
The plate count results were 100 to 1,000 times greater
than the actual sludge or lagoon system plate count results,
this reflecting the higher MLVSS concentration maintained in the
shaft.
304
-------
SECTION VI
ENGINEERING AND ECONOMIC COMPARISONS OF
IDENTIFIED BIODEGRADATION TECHNIQUES
INTRODUCTION
The purpose of this section is to provide design, perfor-
mance, and economic comparisons and evaluations of the biologi-
cal treatment technologies presented in Section IV and Section
V of this report. The applicability of conventional and innova-
tive biological treatment methods described in Section III to
various problematic wastes is also discussed.
The objectives of technology comparisons and discussions
are as follows:
To
wi
ap
o identify robust biological treatment techniques,
ithin defined environmental and waste constraints,
pplicable to a variety of organic materials
t To identify those treatment characteristics which
enhance biodegradation of problematic wastes, so that
they may be more widely applied
t To compare potential secondary impacts on the environ-
ment, including accumulated organic wastes in sludge
materials
• To evaluate the economic factors associated with each
treatment technology, so that effectiveness per unit
cost can be maximized.
It is emphasized that results of comparisons made in this
report are subject to the manner in which evaluation criteria
are weighed. Some of these evaluation criteria, in turn, require
comparative rather than absolute consideration. For example,
when four types of biodegradation technologies are evaluated
according to land requirements, the results are relative to
the technologies considered. This does not mean that the low-
rated technology is land intensive, based on comparison with
the average land requirements of the universe of treatment tech-
nologies. Special mention is also made of the fact that tech-
nology ratings presented in this section imply that conditions
actually existed at the sites described in Sections IV and V.
305
-------
It is emphasized that results of comparisons made in this
report are subject to the manner in which evaluation criteria are
weighed. Some of these evaluation criteria, in turn, require
comparative rather than absolute consideration. For example,
when four types of biodegradation technologies are evaluated
according to land requirements, the results are relative to the
technologies considered. This does not mean that the low-rated
technology is land intensive, based on comparison with the aver-
age land requirements of the universe of treatment technologies.
Special mention is also made of the fact that technology ratings
presented in this section imply that conditions actually existed
at the sites described in Sections IV and V. The sites served
only as single representations of technology applications. Addi-
tional factors include literature data, unpublished data and
communications, and general engineering expertise. The state-
ment that open lagoon systems have a high potential for impact
on air quality, for example, does not imply that the specific
site studied in this project (i.e., 40-Acre Facility) had or did
not have such impacts.
METHODS FOR COMPARING TREATMENT TECHNOLOGIES
The approach to comparisons of studied technologies is shown
in Figure 56. General groups of criteria are first defined,
based on the objectives of the study. Specific comparative cri-
teria are then defined within each group, and applied to the
considered technologies.
General Criteria Groups
The criteria for making engineering and economic comparisons
of biodegradation technologies are included under three general
groups:
• Design
• Performance
• Economics.
Specific Criteria
Specific criteria included in these groups are listed in
Table 111. Most criteria are self-explanatory and wer«e developed
to provide industrial engineers with useful descriptions of each
considered technology.
The variety of construction required (Table 111: Part I,
Item 5) refers to the relative sophistication of each technology.
Activated sludge treatment processes, for instance, usually
require provisions for fabricated clarifier basins, sludge rakes,
and sludge pumping and transfer plumbing. In contrast, some
lagooning operations require relatively few construction acti-
vities for installation.
306
-------
CO
o
Project
Objectives
and
Goals
General Criteria
Groups
• Design
• Performance
0 Economics
Specific Criteria
t Design
0
L..
3.
t Performance
1.
2.
3.
t Economics
1.
2.
3.
Application
to each
Technology
Figure 56. Approach to comparisons of studied technologies.
-------
TABLE 111- SPECIFIC DESIGN, PERFORMANCE AND ECONOMIC CRITERIA
FOR COMPARING BIODEGRADATION TECHNOLOGIES
Part I. Design
1. Scale: Estimated range of system sizes which may be applied to waste-
water stream of similar composition and result in unimpaired treatment
performance.
2. Controlling waste stream design parameters and functions well defined.
3. Availability of data on effects of variations in standard design.
4. Detailed designs and specifications readily available.
5. Variety of construction required.
6. Serviceability of primary system components.
7- Provisions for backup or standby equipment.
8. Provisions for spill basins to divert unacceptable concentrated or
toxic wastes without bypassing untreated to receiving waters.
9. Possible risk of groundwater contamination under certain soil and
geological conditions.
10. Flexible sludge return and/or wasting capacities.
11. Internal system flexibility (e.g. routing of waste flows can be varied).
12. Flow equalization (e.g. storage of wastes prior to treatment) required.
13. Design favors microbial populations which are well adapted for reduction
of problematic industrial organic wastes.
14. System readily operated-automated.
15. Unit processes capable of being sheltered.
16. Ease of construction in varying terrains.
17. Potential for impact on air quality.
18. Potential for impact on visual esthetics (can or cannot be located near
urbanized areas).
19. Amenability of existing design to additions or modifications for upgrading
or increase in capacity.
308
-------
Table 111 (continued)
Part II. Performance
1. Conventional removals.
2. Meeting NPDES limits on current treatment standards.
3. Range of treatable organic wastes.
4. Degree of biotransformation:
amt. in effluents + amt. in sludges
amt. in influents
5. Susceptibility to certain organic toxins.
6. Susceptibility to certain inorganic toxins.
7. Susceptibility to shock loading (concentrated wastes).
8. Rate of 0? transfer.
9. Amount of secondary sludge produced/Kg, of BOD removed.
10. Ease of sludge handling-dewatering.
11. Minimum and maximum tolerable flowrates.
12. Minimum and maximum tolerable loading rates.
13. Incidental removal of non-oxygen demanding materials (metals, salts, etc.)
14. Accumulation of discharged organic materials in receiving waters.
15. Susceptibility to variations in air temperature.
Part III. Economic
1. Land required relative. to other technologies treating similar waste
stream flows.
2. Engineering design costs.
3. Costs of construction (earth moving and erection of structures). Capital
expenses for "off-the-shelf" equipment and installation, and expected
salvage value.
4. Maintenance costs.
309
-------
Table 111 (continued)
5. Supervision and labor costs.
6. Chemical costs.
7. Energy costs - (electricity and fuel).
8. Total cost amortized over expected lifetime and expressed in terms of
kilograms of various removed constituents.
9. Cost increases with increased scales.
10. Costs of ultimate disposal of secondary wastes (air, emmisions, and
sludge).
310
-------
Serviceability of system components (Part I, Item 6) refers
to several factors, including ease of access to components, man-
hours and level of training required for maintenance personnel.
Provisions for backup or standby equipment (Part 1) and spill
basins (Part 1) refers to the amenability of the treatment tech-
nology to installation of such equipment. It does not imply
the presence or absence of such equipment at the specific case
study sites described in Section IV.
The "conventional removals" criteria listed in Part II
refers to the reduction of the following waste parameters dis-
cussed in Section IV:
Total Organic Carbon (TOC) Chloride
Chemical Oxygen Demand (COD) Sulfide
Biological Oxygen Demand (BOD) Phosphorus
Total Suspended Solids (TSS) Total Nitrogen
Volatile Suspended Solids (VSS) Various Metals
Total Dissolved Solids (TDS) Oil and Grease.
The "range of treatable organic wastes" applies to reduction
of specific organic waste constituents reported in Section V of
this report.
The estimated degree of biotransformation of organic waste
materials (Part II, Item 4) is important because it considers
the potential for accumulations of recalcitrant organic compounds
in sludges. Total biotransformation is, then, taken to be the
ratio of effluent sludge waste concentrations to the influent
concentrations. Waste accumulations in sludges may result in
environmental problems at land disposal or incinerator facili-
ties.
The susceptibility to organic or inorganic toxins or shock
loading (Part II, Items 5, 6, and 7) indicate system stability
under varying waste conditions. Shock loading is differentiated
from fluctuations in toxin content in that the former can be
caused by high concentrations (e.g., extremely high COD or BOD)
of organic compounds which are not detrimental to the plant biota
in usual and expected concentrations. Toxins, on the other hand,
are wastes which are not usually present or present only in
dilute concentrations which increase in concentration unexpec-
tedly.
COMPARISONS OF CASE STUDY TECHNOLOGIES
Design
Both the pure oxygen UNOX and Deep Shaft systems were found
to be equally superior from a design standpoint. This is due
primarily to controlled sludge production, favoring of accelera-
ted microbial metabolism through innovative techniques, and the
fact that both systems are closed and relatively compact. They
311
-------
are also easily supervised and readily adaptable to a variety
of terrains. Unique positive design attributes of Deep Shaft
technology include excellent sludge control and minimization of
sludge production, ease of system automation, and minimal impact
on visual aesthetics and air quality. The UNOX system had almost
the same positive attributes. UNOX is somewhat more difficult
to house and protect from colder air temperatures, but is not
as dependent upon proper site selection based on geological char-
acteristics.
Performance
All monitoring and special testing data for organic waste
reduction, as evidenced in this report, indicate that the series
lagoon system was superior to other treatment methodologies in
removing the broadest range of organics with the highest level
of biodegradation. The lagoon system was also superior in terms
of sustaining shock loadings and large fluctuations in flow rates.
Lagoons did not measure up to other techniques only in the rate of
02 transfer and impact of air temperature.
Economic
Series lagoon systems are most desirable in terms of econo-
mic criteria. Series lagoons are found to be above average for
all specific cost criteria except land requirements and cost
variations with scale-
Under conditions where land is extremely expensive or not
available, or where smaller flow rates are involved (less than
1 MGD), the most attractive alternative to series lagoons for
treatment of industrial waste streams is the Deep Shaft. It is
both land conserving and applicable to a wide variety of flow
rates. Deep Shaft technology has been found to be average or
better than average according to all cost criteria except con-
struction costs and cost per unit of waste removed. The addi-
tional construction costs over other conventional technologies
are primarily due to the requirements for shaft drilling and
lining. Nevertheless, the slightly higher initial capital invest-
ments tend to be offset by lower annual and recurring costs such
as maintenance, supervision and labor, and chemical and energy
costs.
The higher estimate for cost per unit of waste removed is
based upon limited information about the application of Deep
Shaft technologies to recalcitrant organic materials. The tech-
nology is relatively new and cost information was available only
for a smaller scale plant treating a highly variable flow. Sec-
tion IV shows the cost of waste constituent removal expressed as
kg of BOD to be $2.6 ($26/lb), compared to $0.11 ($0.11/lb) for
series lagoons and $0.55 ($0.55/lb) and $0.22 ($0.22/lb) for the
312
-------
studied UNOX and activated sludge facilities, respectively. Based
on the economic criteria, the removal cost for future, full-scale
Deep Shaft applications will probably approach $0.13/kg ($0.13/lb)
of BOD.
Another observation which can be drawn from the economic
comparisons is that both of the innovative technologies, Deep
Shaft aeration and pure oxygen aeration, compete favorably with
the more widely applied conventional activated sludge systems.
This would indicate that as these new technologies are developed
and additional information is available on their applicability
to industrial waste streams, they will be more widely applied
to national waste flows.
RECOMMENDED IMPROVEMENTS FOR BIODEGRADATION
OF ORGANIC MATERIALS
A primary objective of this study is to indicate how exist-
ing biodegradation systems can be upgraded to improve treatment
of organic wastes. Such recommendations are based upon insights
derived during this study.
The primary operational and/or design improvements should
be aimed at overcoming organic and hydraulic over 1oadings, improv-
ing treatment of specific organic constituents, and/or meeting
more stringent treatment requirements (25).
Federal and state government agencies presently require
industrial waste treatment facilities, both generator-owned and
publically-owned to comply with discharge standards. Although
present standards stipulate BOD, COD, TOC, and SS removals, it
is possible that in the near future these indicators of organic
waste materials may be accompanied by new demands for removal of
specific organic constituents. The "priority pollutants" asso-
ciated with the Consent Decree (26) are presently being analyzed
in a variety of industrial discharges so that specific hydrocar-
bon and chlorinated organic solvent discharges to the environment
can be controlled.
Increased hydraulic and organic loadings or sudden increases
in toxic waste constituents can have a significant impact on the
overall efficiencies demonstrated by biological treatment systems.
Increased process waste streams or other industrialization asso-
ciated with treatment plant influents can cause such increases
or fluctuations.
Overloads created by industrial contributors can be relieved
by pretreatment, by equalization, or by expansion of critical
plant components. Equalization of industrial flows by the dis-
charging industry is especially effective when the discharge is
concentrated but of relatively short duration (27).
313
-------
Primary Aerobic Stabilization-Equalization
During the execution of the field study portion of this pro-
ject, it became evident that industrial influents, to biological
waste treatment plants were characterized by periodic changes in
volume, strength, and composition. All these changes can have a
detrimental impact on maintaining desirable biooxidative condi-
tions in the plant. To lessen the chance for system upset, sys-
tems should be operated as uniformly as possible. Flow equali-
zation is one means whereby changes in waste quantities and quali-
ties can be dampened and concentrated sludge discharges can be
mixed with dilute wastes in some types of storage vessel or basin,
Equalization storage may be located at the site of waste
generation, in collection or transfer piping, and at the influent
point(s) of the treatment system. Equalization basins have not
been fully applied in industrial wastewater collection systems
and represent a great potential for improving the quality of con-
tributor-treatment networks and enhancing overall treatment. Spe-
cially designed subsurface equalization basins with lift stations
may be installed at key points along the collection system and
preceded by bar screens and a grit chamber to avoid solids accum-
ulation. Such basins can also be installed at the treatment
plant, minimizing head loss and making use of existing pretreat-
ment facilities. Facilities should be provided at equalization
basins for periodic removal of settled solids.
It should be noted that flow equalization systems also
increase the total volume of the collection and treatment system.
Substantial increases in retention time, in turn, will allow for
more complete biodegradation of recalcitrant organic materials.
To maximize the opportunity for biological stabilization in the
equalization basin, it is advisable to provide oxygen and bac-
terial seed. Aeration of raw' influents and contact with activa-
ted sludge from downstream processes would provide such an envi-
ronment. The impact of generated biological floes from the sta-
bilization basin on primary settling characteristics needs to be
studied further.
Another method of providing flow equalization and biological
"roughing" treatment prior to the main treatment works Js to
install a small deep shaft aeration facility between th*e pre-
treatment works (e.g., bar screen, grit chamber, and comminutor)
and the primary facility. Primary settling would then be best
achieved by an air flotation unit with surface and bottom sludge
rakes. Figure 57 shows two conceptual industrial waste treatment
systems utilizing primary aerobic equalization-stabilization
units.
314
-------
BAR GRIT /^ ~X
„ _rrf, CHAMBER / \
INFLUENT EQUALIZATION [ PRIMARY
' *" *" 1*"" STABILIZATION *"( SETTLING/ f
>—... P . \ /
\ / 1
ISLUDGE '
| RE TURN ' IRE
S T
1 t
WASTE SLUDGE
DEEP SHAFT
BAR GRIT AERATOR
r THAMRFR ^ ^
•^ ^- K C. t IN | / X
INFLUENT / f~^\ \
-^^ ,-^fc , ;^,. 1 f 1 l.__i_^^toi ATP? I~I HTATlnri ii^^
_ ^ \ / %
1 1
i i '
RETURN . '
ISLUDGE , |SL
AERATI ON
BASIN
-UDGE
:TURN
:s
AERATION
BASIN
ETURN
.UDGE
S T
t T
WASTE SLUDGES
a EFFLUENT
^
1
j
j SECONDARY AFFLUENT
^"l SETTLING / "^
1
J
Figure 57. Two conceptual industrial waste treatment systems utilizing
primary aerobic evaluation stabilization units.
-------
Primary Anaerobic Digestion-Equalization
Primary treatment in anaerobic equalization basins has also
been effective in treating petrochemical wastes. Such basins
are particularly effective in treating low molecular weight acids
and alcohols (28). Odorous sulfur compounds often associated
with industrial waste streams can also be stabilized by anaero-
bic treatment.
Spi11 Basins
Spill basins serve as special types of equalization basins,
accommodating, storing, and treating overflow volumes of con-
centrated sludges in the treatment plant influents. Since spill
basins are not on-line with the continuous waste flow, special
overflow weir or sensor-actuated flow gates must be provided for
temporary diversion of flows to the basin structure. In cases
where the basin is to be used for hydraulic equalization only,
some types of overflow structure is required. Where the basin
is used for protecting the on-line biological treatment processes,
some method must be provided for anticipating qualitative changes
so that the volume which must be diverted before the normal treat-
ment scheme can be restored.
Typically, spill basins are used at industrial waste treat-
ment facilities when there has been an unexpected discharge fluc-
tuation at one of the waste contributors. Such changes can be
caused by in-plant spills, improper process control, or irregu-
lar activities such as system shutdowns, vessel washings, or
purging of in-house storage tanks. Usually, when these occurren-
ces result in irregular waste discharges, plant personnel will
immediately warn the treatment plant operator to expect a change
in influent characteristics. Such a system usually provides
enough lead time to divert the waste stream to the equalization
basin and avoid system upsets. Nevertheless, in-stream monitor-
ing devices for detecting radical changes in organic waste con-
centrations should be developed and used at key points in indus-
trial waste collection systems to alert plant operators to poten-
tial overload ings.
Once a volume of waste is diverted to the spill basin, it
must be biologically and/or chemically stabilized and fhen intro-
duced slowly into the regular treatment plant flow. In extreme
cases, spill basins are emptied by vacuum truck, and wastes are
transported to special off-site disposal facilities.
The cost of equalization-stabilization on spill basin sys-
tems will vary considerably, depending on volume requirements,
construction methods, and auxiliary equipment such as piping,
aerators, liners, land costs, and pumping requirements. Capital
costs for equalization facilities have been estimated by various
authors and are shown in Table 112.
316
-------
TABLE 112. COST OF EQUALIZATION FACILITIES (27)*
Basin
Size
(MG)
0.32
0.88
2.40
Earthen
with
pumping
$ 165,000
226,000
423,000
Basin1"
without
pumping
$ 96,000
112,000
178,000
Concrete
with
pumping
$ 223,000
443,000
1,037,000
Basin
without
pumping
$ 165,000
329,000
792,000
* All costs updated to 1977 dollars from 1974 (10 percent interest).
t The construction cost for the earthen equalization basin includes
excavation, plastic liner, sand subbase, concrete screen pad, dike
fill, underdrain, and floating aerator.
317
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Neutralization
The acidity or alkalinity (pH) of the waste stream intro-
duced to the bioreactor must be maintained within a specific
range if microbial populations are to be favored. To accomplish
this, different industrial waste streams may be selected for
treatment based on their neutralizing effects, or chemicals may
be purchased and added to the influent wastes. In the former
situation, lower operational costs are realized (no chemicals
must be purchased), but maintaining the desired pH depends upon
the regular flows of each component stream. The stockpiling of
chemicals such as sulphuric acid, caustic soda or lime will
increase chemical costs but will also provide the capability for
adjusting chemical additions based on variations in waste stream
characteristics. A relatively sophisticated control system can
be applied if the variability is high (74, 97). Neutralization
of highly concentrated waste streams may be most effectively
achieved before they are mixed with other, more dilute waste
streams. Design of an industrial waste treatment facility should
include a careful evaluation of all influent waste streams to
determine the most cost-effective and reliable method for pH con-
trol .
Nutrient Addition
The addition of nutrients required by microbes for efficient
biooxidation of carbonaceous substrates was found to be a valua-
ble technique for enhancing treatment efficiency. Many petro-
chemical, textile, and other industrial wastes are deficient in
nitrogen and phosphorus and must be supplemented if biodegrada-
tion is to be the primary method of treatment. The advisable
carbon-to-nitrogen-to-phosphorus (C:N:P) ratio for aerobic bio-
conversion is approximately 100:10:1.
Nutrient deficiencies may be overcome in the same manner
as discussed for pH control: by chemical addition or by care-
ful selection of influent contributors to ensure a proper balance
As shown in Section IV, major industrial treatment facilities
have realized large savings in chemical costs by combining nutri-
ent-deficient waste streams with others having high concentra-
tions of phosphorus compounds or ammonia. The inclusign of a
municipal waste stream in industrial influents is another valua-
ble method of providing these materials.
Bacterial Seeding
The maintenance of specially adapted populations of micro-
organisms by initial or continuous seeding with specially pre-
pared cultures has not played a significant role in enhancing
the treatment efficiency of industrial waste treatment plants.
The microbial populations of such treatment systems are highly
varied and are controlled, in part, by environmental conditions
318
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established by plant design, waste characteristics, operational
techniques, and competing biota in the same regions of the plant.
The presence of a homogeneous culture not directly favored by
all these conditions can only be maintained through constant
addition of cultures prepared outside the treatment plant envi-
ronment. This maintenance of an artificial population is usually
expensive and of doubtful effectiveness. Biological seed from
municipal waste treatment facilities will usually contain all
microbial species necessary for biodegradation of a wide variety
of industrial wastes.
Extensive Aeration
Aeration of industrial wastes is an important technique in
enhancing biodegradation of organic constituents. However, oxy-
gen transfer is only of secondary importance in treating recal-
citrant wastes with low rate constant (k) values. Some wastes,
such as oils and alcohols, will only be degraded after long peri-
ods of contact with activated sludge. This appears to be due to
the competition of these materials with more readily degradable
organic compounds and requirements for development of special
enzymes by some microorganisms before metabolism can be initia-
ted. A long retention time such as that provided by equalization
or spill basins must be coupled with efficient oxygen transfer
into the waste materials.
Activated Carbon
Activated carbon may be used either in column filtration
units or as a powder added directly to the bioreactor to adsorb
certain organic materials and provide a concentrating substrate
for microbiological activity. In certain cases, such practices
may effectively remove toxic components not readily treated bio-
logically and may reduce the need for retaining entire waste
volumes for extended periods of time.
It has been noted that there are few current applications
of this promising technology (27). Experience has shown that
typical treatment costs for activated carbon addition can vary
from 0.4 to 1.8 cents/1,100 a. Research and development should
be continued in order to increase the regenerative capacity for
spent powered carbon.
Temperature Control
Many industrial waste streams, particularly those from petro
chemical or kraft mill processes, may reach the treatment facil-
ity at elevated temperatures. If these wastes are not cooled to
at least 4QOC to 45oc, they may adversely affect the microorga-
nisms in the bioreactor.
319
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The use of cooling towers should be considered as an effec-
tive means of enhancing stable biodegradation and favoring diverse
microbial populations.
Other Pretreatment Techniques
Other pretreatment techniques may also be practiced in order
to enhance the biodegradation of problematic organic waste streams.
Most of these are physical/chemical treatment processes and are
outside the context of ^biodegradation. Nevertheless, their use
in conjunction with biological treatment can greatly improve the
overall treatment capabilities.
The pretreatment technologies may be applied to wastes prior
to their introduction to the biological treatment processes to
eliminate or reduce the total loading of carbonaceous materials.
Some technologies, such as solvent extraction, are best applied
to single-process waste streams before they are discharged into
the industrial collection system for transport to the plant. Other
techniques applicable to single or mixed waste flows include
reverse osmosis, chemical precipitation, evaporation, ion exchange,
distillation, resin adsorption, and density separation. Additional
research should be conducted to determine how these treatment
techniques may be used in association with biological treatment
to provide required effluent qualities.
320
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SECTION VII
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•
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336
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APPENDIX A
BIBLIOGRAPHY OF PERTINENT LITERATURE
PERTAINING TO MICROBIAL DEGRADATION OF ORGANICS
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341
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APPENDIX B
SAMPLING AND ANALYSIS: PARAMETER AND
STATION SELECTION
SELECTION OF ORGANIC TOXINS FOR SAMPLING AND ANALYSIS
The method of selecting candidate organic constituents for
quantitative analysis for each site is shown in Figure B-l.
Information from previous industrial surveys was tested according
to the selection criteria, and a list of potential organic waste
stream constituents was developed (113). Table B-l is a list of
waste products developed for the petrochemical industry.
Once such lists were developed for each of the industrial
contributors, specific hazardous organic compounds were identi-
fied and their toxicity determined from appropriate literature
(104, 113, 119, 129). The resulting candidate hazardous organic
waste stream constituents for each site are shown in Table B-2.
The compounds marked with an asterisk (*) in this table were
selected as candidates for sampling and quantitative analysis
because they are slightly or moderately soluble in water and are
potential water contaminants. In addition, these compounds may
be analyzed with gas-liquid chromatography on either a polar or
nonpolar column system. Ethers, aldehydes, glycols, acids, and
nitriles without alpha-H atoms were excluded because of their
relatively low toxicity and intermediate or extreme polar charac-
teristics. Analysis of such materials would require additional
retooling of the gas chromatograph, adding significantly to the
cost of the tests.
Table B-3 shows the classes of compounds considered for final
selection. Again, most "polar" and "intermediate polar" classes
were excluded for the sake of .ease of analysis. Table B-4 shows
the 20 compounds finally selected and their designation as either
"polar" or "low or nonpolar." „
In addition to the 20 organic compounds quantitatively anal-
yzed by gas chromatography, 109 organic compounds were analyzed
for their occurrence in the waste stream by gas chromatography/
mass spectrophotometry (GC/MS). These organics are shown in
Table B-5.
SELECTION OF BIOLOGICAL PARAMETERS FOR ANALYSIS
Microorganisms, bacteria, fungi, algae, protozoa, and viruses
can be present in wastewater. Moreover, representatives of all
but the viruses are capable of proliferating in wastewater.
According to classical ecological theory, a mixture of a wide
342
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TYPES OF INDUSTRIES AND ASSOCIATED PROCESSES/EACH FIELD SITE
,> ^INORGANIC WASTES (EXCEPT ORGANO-METALLICS)
GENERAL CLASSES AND AMOUNTS OF ORGANIC WASTES/INDUSTRIAL CONTRIBUTOR
^.NON-TOXIC OR SIMPLY HAZARDOUS
~(e.g., EXPLOSIVE) WASTES
GENERAL CLASSES OF ORGANIC TOXINS (e.g., CHLORINATED HCs, PHENOLICS, ETC.)
NON-SPECIFIC DATA
SPECIFIC TOXIN COMPOUNDS
NON-INDICATOR COMPOUNDS
SPECIFIC TOXINS AS INDICATORS OF CLASSES OF ORGANIC TOXINS
DETECTION METHOD PROHIBITIVE OR DIFFICULT
KNOWN METHOD OF DETECTION
-^COMPOUND IS NON-DETECTABLE
COMPOUND PRESENT INDETECTABLE QUANTITY
NOT A FINAL PRODUCT - INTERMEDIATE ONLY
COMPOUND IS A FINAL PRODUCT (e.g., SOMETHING THAT MIGHT
BE STORED)
EXTRANEOUS CLASSES
RE-APPRAISE THE GENERAL CLASSES OF ORGANIC TOXINS
Figure B-l. Method of selection for candidate
organic constituents for analysis.
343
-------
TABLE B-l. POTENTIAL PETROCHEMICAL WASTE PRODUCTS
Cyclohexanol
Toluene 2,4-diamine
Acetaldehyde
Acetic acid
Acetic acid salts; copper
acetate; potassium; zinc
Acetone
Acetylene
Acrylonitrile
Butanol-N
Butanol-sec
Carbon tetrachloride
Chloroform.
Diethylamine
Ethanol (28695)
Ethylene
Ethylenediamine
Ethy1eneimine
Ethyl chloride
Ethylene dichloride
Ethylene glycol
Ethylene glycol diacetate
Ethylene oxide
Formaldehyde
Formic acid
Formic acid, sodium salt
(sodium formate)
Glutamates
Glycol ethers
Hexanediamine (1,6-hexa-
methylenedi ami ne)
Isopropyl ether
Methanol
Methylamines
Methylene chloride
Methyl chloromethylether
Methyl acetate
Methyl chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Propylene
Propylene chloride
Propylene glycol
Propylene oxide
Vinyl acetate monomer
Vinyl chloride monomer
Xylene propanol
344
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TABLE B-2. CANDIDATE ORGANIC TOXIC CONSTITUENTS FOR
FIELD SAMPLING AND LABORATORY ANALYSIS
Washburn Tunnel
Facility
benzene*
phenol*
cresol*
toluene*
xylene*
xylenol*
hexanol*
acrylonitrile*
40- Acre
Facility
benzene*
phenol*
ethyl benzene*
styrene*
butanol*
ethyl ene
dichloride*
hexanol*
methanol*
Deep Shaft
Paris, Ont.
benzene*
phenol*
toluene*
butanol*
ethyl ene
dichloride*
methanol*
isopropanol*
acetonitrile
diacetate
formaldehyde
formic acid
methanol*
methyl acetate
methyl chloride*
methyl
methacrylate
carbon
tetrachloride*
butyl mercaptan*
ethyl mercaptan*
methyl mercaptan*
n-and isopentanol*
n-and isopropanol*
ethylene glycol
monomethyl ether
carbon
tetrachloride*
formaldehyde
various
proprietary dyes*
345
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TABLE B-3. GENERAL CLASSES OF ORGANIC TOXINS FOR ANALYSIS
IN FIELD SAMPLES
Polari ty
Most polar
Polar
Intermediate
pol ar
Low polarity
Non-pol ar
Class
glycol s
acids
alcohol s
phenol s
nitriles with
alpha-H atoms
ether
nitriles without
-H atoms
aldehyde
CH3C1
CH2C1CH2C1
aromatic hydro-
carbons
mercaptans
CC14
# of Compounds
1
3
7
3
1
1
1
1
1
1
5
3
1
per Class
4
11
3
7
4
other chlorinated
HC's
346
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TABLE B-4. FINAL LIST OF CONSTITUENTS FOR
ANALYSIS AT THE FOUR FIELD SITES
Washburn Tunnel
Facility Group*
Benzene
Phenol
Cresol
Toluene
Xylene
Xylenol
hexanol
Acryloriitrile
Methanol
Methyl chloride
Carbon tetra-
chloride
Butyl mercaptan
Ethyl mercaptan
Methyl mercaptan
2
1
1
2
2
1
1
1
1
2
2
2
2
2
40-Acre
Facility Group*
Benzene
Phenol
Ethyl benzene
Styrene
Butanol
Ethyl ene
dichloride
Hexanol
Methanol
n-and iso-
petanol
n-and iso-
propanol
2
1
2
2
1
2
1
1
1
1
Deep Shaft
Paris, Ont. Group*
Benzene
Phenol
Toluene
Butanol
Ethyl ene
dichloride
Methanol
Isopropanol
Carbon tetra-
chloride
2
1
2
1
2
1
1
2
1 = Polar compounds
2 = low or non-polar compounds
347
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TABLE B-5. LIST OF ORGANICS ANALYZED BY GC/MS
I. PESTICIDES
Acrolei n
A1 d r i n
-BHC
-BHC
-BHC (Lindane)
-BHC
Chiordane
ODD
DDE
DDT
Die!dri n
-JEndosul fan
-Endosu1 fan
Endosu1 fan sulfa te
E n d r i n
Endri n a 1 dehyde
Heptachlor
Heptachlor e p o x i d e
I sophorone
TCDD (2,3,7,8-tetrachlorodioenzo-p-dioxin)
Toxaphene
II. PCB's AND RELATED COMPOUNDS
PC
PC
PC
PC
PC
PC
PC
2-
B-l
B-l
B-1
B-l
B-l
B-l
B-l
Chi
0
2
o
16 (
21 (
32 (
242 (
2
2
2
0
48 (
54 (
60 (
rona
Aroc
A roc
Aroc
Aroc
Aroc
Aroc
Aroc
h
h
h
h
h
h
h
phtha
1
1
1
1
1
1
1
1
0
0
0
0
0
r
r
r
r
r
or
0
e
r
ne
1
1
1
1
1
1
1
016)
221)
232;
242)
248)
254)
260)
III. HALOGENATED ALIPHATICS
Methane, bromo- (methyl bromide)
Methane, chloro- (methyl chloride)
Methane, dichloro- (methylene chloride)
Methane, chlorodibromo-
Methane, dich1orobromo-
Methane, tribromo- (bromoform)
Methane, trichloro- (chloroform)
Methane, tetrachloro- (carbon tetrachloride )
Methane, trichlorofluoro-
Methane, dichlorodifluoro-
348
-------
TABLE B-5 (continued)
Phenol , 2 , 4-d i n itro-
Phenol , 2 , 4-dimethy1 -
m-Cresol, p-chloro-
o-Cresol, 4,6-dinitro-
VII. PHTHALATE ESTERS
Phthalate, dimethyl-
Phthalate, diethyl-
Phthalate, di-n-butyl-
Phthalate, di-n-octyl-
Phthalate, bis(2-ethylhexy1)-
Phthalate, butyl benzyl-
VIII. POLYCYCLIC AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Benzo(a)pyrene
Chrysene
Dibenzo(a,n)anthracene
Fluoranthene
F1uorene
Indeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
IX,. NITROSAMINES AND OTHER N I TROGEN-CONTA IN I NG-COMPOUNDS
Nitrosamine, dimethyl- (DMN)
N i t r o s a mi n e , di p he n y1
Nitrosannne, di-n-propyl-
Benz i d i ne
Benzidine, 3,3'-dichloro-
Hydrazi ne, 1,2-diphenyl-
Aery 1 on i tri 1 e
349
-------
variety of substrates will support a rich and varied population;
conversely, single substrates will, by selective pressure, give
rise to a restricted population (3). Studies have presented
information on the tremendous diversity of the microbiological
flora present in municipal wastewater treatment systems (69), yet
similar information for microbial type or number in industrial
wastewater treatment is limited (153).
Studies on microbes in industrial treatment systems have
reported the predominance of one or a few microbial species (30,
83, 153). These are in agreement with the above premise that the
small number of substrates found in industrial wastewater restricts
the diversity of the microbial population. The microbiological
portion of this study was designed to test this premise at the
treatment facilities surveyed and determine which, if any, micro-
bial group predominates and the organic substrates utilized by
specific microbes.
STATION SELECTION AND SAMPLING FREQUENCY
Both the location of sampling stations and sampling frequency
we re chosen to aid in characterizing biological treatment of hazar-
dous organic materials. In general, sampling stations within the
treatment systems were selected to indicate the changes in the
waste streams as they pass through the unit treatment processes
and are discharged to the receiving environment.
Sediment sampling sites at and adjacent to the treatment
facilities outfalls were selected to detect either the presence
or accumulation of organic compounds. These sites were located
with an understanding of the receiving body hydrology in relation
to net flow (drainage of uplands) and cyclic effects of tidal cur-
rents. These relationships were used to estimate the maximum
upstream displacement of constituents from the outfall. The con-
trol sediment sampling sites were located just upstream of that
point. Figure B-2 is a schematic of the sediment sampling sites
locations.
SAMPLING METHODS
Many factors must be considered in devising a sampling regime
which will result in representative samples and meaningful con-
clusions. Ideally, the influent-effluent and in-plant waste stream
characteristics would be constant under such conditions, and the
process could be characterized with relatively few replicate sam-
ples. However, most contributing industries discharge certain
waste materials intermittently and are continuously changing pro-
cess flows during operation. Furthermore, processes in the waste
treatment plant itself can make it difficult to compare effluent
constituent levels with known influent values. Changes in opera-
tion and efficiencies of the various units and complete mixing
in the process flow are major causes of this problem. Figure B-3
shows how one fluctuating constituent in a plant effluent might
be affected.
350
-------
NET TIDAL DISPLACEMENT
POTENTIAL
SPRING
TIDE
MAX.
CO
in
CHANNEL FLOW
CONTROL
SITE
I
-I
OUT FALL
SITE
Figure B-2. Location of control and outfall sediment samplinn sites.
-------
CO
en
no
INFLUENT
SAMPLING
EFFLUENT
SAMPLING
C- —-^ NET AVG .
REMOVAL
AVG.l = AVG.2
Figure B-3. Hypothetical fluctuation of one constituent in-plant influent-effluent.
-------
In sampling waste streams, there are certain variables which
must be considered in identifying various trace organic constitu-
ents. Independent variables are:
• Changes in industrial discharges
• Changes in plant operations/efficiencies
• Treatment plant retention time.
Dependent variables are:
• Rate of sampling (e.g., 1/hr, 12/day, I/day)
t Duration of sampling period (e.g., 1 day, 1 wk, 2 wk).
In systems such as wastewater treatment plants, independent
variables fluctuate to such an extent that characterization of
the waste stream constituents by a few replicate samples is mean-
ingless. Therefore, the best estimate of a waste constituent
average value can be found by controlling the dependent variables
and taking numerous small composite samples over an extended
length of time. Although many of the specific details concerning
hourly, daily, or weekly fluctuations may be lost, composite samp-
ling greatly reduces the number of analyses and amount of labor
involved as compared to numerous individual grab samples. How-
ever, where composite sampling was not feasible, e . p . , sampling siudge
from secondary clarifiers with fluctuating sludge blanket heights,
grab sampling was used.
Composite Sampling
For a representative determination of trace organics in
industrial waste streams, provisions must be made for restricting
biodegradation of the organic compounds before analyses can be
performed. The most popular procedure for stopping biodegrada-
tion during composite sampling is refrigeration of the sample.
This principle was incorporated into the composite sampler design
through immersion of the sample in an ice bath within an insulated
container. With this setup, the sample temperature was maintained
at 3°C to 5°C during the duration of the composite sampling per-
iods.
Figure B-4 shows the composite sampler equipment. Plate 1
is a close-up view of the equipment in operation at a field loca-
tion. The composite sampler pump flow is 4 £/min. A T-fitting
allowed for draw-off of a portion of the sampler flow to a brown
glass bottle in the insulated cooler. The composite samplers
were set up to draw 4 aliquots of approximately 35 m£ each per hr.
This gave a 24-hr sample volume of 3.36 a.
Care was taken to ensure continuous composite sampling, even
during periods of low flow, by using a sampler influent tubing
long enough to remain immersed in the waste stream. Sampling
353
-------
1. SURVEYOR AUTOMATIC COMPOSITE SAMPLER
110V N-CON SYSTEMS CO.
2. SAMPLER EFFLUENT TUBING (0.6 Cm I.D.
POLY'ETHYLENE ) WITH T-FITTING AND 0.3 Cm
I.D. DRAW OFF TUBING TO SAMPLE BOTTLE
3. 3.8 LITER BROWN GLASS BOTTLE, HEXANE
WASHED
4. SAMPLER INFLUENT TUBING (0.6 CHI I.D.
POLYETHYLENE) 0.45 KG WEIGHT AT ONE END
5. 11.4 LITER PLASTIC INSULATED COOLER
Figure B-4. Composite sampler equipment.
354
-------
points were located in areas of turbulence to ensure representa-
tive completely mixed samples. Samples were removed daily, and
the ice bath replenished.
Grab Sampi ing
The sampling schedule necessitates frequent grab sampling at
different locations. A sampler which required cleaning after each
use, e.g., a Van Dorn Bottle, could not be used. Therefore, a
grab sampler was devised which would allow rapid, repeated samp-
ling of wastewater without repeated washing. The grab sampler
consists of a sampler body with attached nylon rope line and was
constructed of 10.2-cm (4-in) diameter polyvinyl chloride pipe
(PVC) and pipe caps (Figure B-5). One end was threaded for easy
removal of the pipe cap. Thus, clean sample bottles could be
inserted into the sampler quickly and filled directly by lowering
into the waste stream. A stopper with an attached line and neces-
sary ballast was used when samples were taken at various deaths
in the wastewater stream. The grab sampler is 215.4 cm (10 in)
long and weighs 3.2 kg.
Sediment Sampler
A La Motte Bottom Sampling Dredge was used to obtain samples
of bottom sediment. The dredge is 20 cm (7 in) long, 7 cm (2.75
in) in diameter, and retrieves a sample volume of 0.77 a.
SAMPLE TRANSPORTATION AND PRESERVATION
Two types of containers were used to hold the samples for
storage and shipment. One-liter brown glass jars were used for the
organic analysis samples, while biological samples were stored
and shipped in one-liter polyethylene cubitainers.
All samples were shipped in ice and packed in insulated con-
tainers.
ANALYTICAL METHODS
Chemical Analysis
The organic analyses by gas chromatography (GC) and gas
chromatography/mass spectrometer (CG/MS) were completed essen-
tially according to the procedure described in the EPA protocol
for sampling and analysis of industrial effluents (158). For
analyses of organic compounds not covered by EPA protocol, the
samples were extracted at pH 11, then pH 2. Each of the extracts
were then combined and concentrated in a Kuderna-Danish (K-D)
evaporation apparatus. The concentrated extract was then injected
into a gas chromatograph unit equipped with a flame ionization
detector (GC-FID). The same analytical parameters were used as
specified for the Protocol base/neutral fraction analysis.
355
-------
1. HARD RUBBER STOPPER WITH ATTACHED NYLON
LINE
2. THREADED PIPE CAP, PVC, 10.2 Crtl DIAMETER
3. 1 LITER BROWN GLASS BOTTLE, HEXANE WASHED*
4. COMPOSITE SAMPLER BODY, PVC, 10.2 Cm
DIAMETER, 19 Cm LENGTH
5. COMPLETE GRAB SAMPLER UNIT WITH ATTACHED
NYLON LINE
Figure B-5. Grab sampler equipment.
356
-------
In the VGA procedure, the Bellar and Lichtenberg hardware
was employed. Instead of interfacing this hardware with the GC/MS,
the syringe was inserted into the septum of the gas chromatograph.
Conditions were otherwise in accordance with EPA Protocol. As in
the semivolatile analyses, assignments were made on the basis of
single-column retention volumes.
Analysis of purgeables in sediment samples was conducted in
accordance with the technical intent of EPA's "Chemistry Labora-
tory Manual/Bottom Sediments." Although this manual does not
treat the VOA subject, it specifies analysis of ornanics in the
"standard elutriate," or water analytically brought into contact
with the sediment sample. This was done by adding a measured
volume of water to furnish an ullage-free supernatant over about
an equal volume of sediment contained in a centrifuge tube. A
septum was then afixed and the tubes shaken for 30 min. Following
this, the tube was centrifuged and the supernatant tested in the
usual EPA Protocol manner.
Sludge samples, containing only a low level of solids, were
handled as liquids. Although the solids contents were determined,
constituent levels have been expressed on a weight/volume basis.
Microbiological Analysis
Microbiological analyses of the biological sludges from the
studied treatment facilities were undertaken to identify the gen-
eral groups of microbes present, the relative concentration of
microbes, and the growth of isolated microbes on selected carbon
source media.
Wet mounts and gram-stain smears were prepared upon receipt
of the samples at the laboratory. Following complete mixinn of
the samples to disperse solids, dilutions were prepared in 0.01-
percent peptone water blanks. Aliquots were then taken for Most
Probable Number (MPN) determinations and for plate counts. For
the MPN procedure Standard Methods, lactose broth was employed
(10 nu/tube plus a durham tube). One-mi 11i1iter samples ofthedilu-
tions were introduced and the tubes were incubated at 35°. Gas forma
tion was observed in accordance to the recommended procedure (148).
MPN results are in terms of estimated total coliform popula-
tion. Gas positive tubes were subcultured to eosin-methylene
blue (EMB) agar and held for 24 hr at 35°C. Subsequent observa-
tion of the EMB plates was done to identify typical colonies
(Escherichia c o1i , Enterobacter, possibly Salmonella or Shigella,
etc. ) .
Plate counts were determined using Standard Methods Agar (10)
with two plates per dilution. Total plate counts were reported
in terms of 5 days incubation at 24°C. Representative colonies
were picked and maintained on slants under refrigeration for later
357
-------
determination of carbon source utilization. The existence of an
autotrophic microbe (sulfur-iron oxidizing bacteria) was confirmed
by inoculation of thiosulfate-mineral salts medium and ferrous
iron-mineral salts medium.
358
-------
TECHNICAL REPORT DATA
(Please read /HUnictions on the reverse before i
1. REPORT NO.
11^600/2-79-006
4. TITLE AND SUBTITLE
SELECTED BIODEGRADATION TECHNIQUES FOR TREATMENT
AND/OR ULTIMATE DISPOSAL OF ORGANIC MATERIALS
7. AUTHOR(S)
SCS Engineers
9. PERFORMING ORGANIZATION NAME AND ADDRESS
SCS Engineers
4014 Long Beach Boulevard
Long Beach, California 90807
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory--Cin.,OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
March 1979 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1DC618
11. CONTRACT/GRANT NO.
Contract No. 68-03-2475
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officer: Charles J. Rogers 513/684-7881
16. ABSTRACT
Organic constituents in aqueous process effluent from various industries often
have properties not readily treatable by conventional biological processes. These
properties include high COD/BOD ratios, low nutrient content, biocidal content, mar-
ginally degradable constituents, and a tendency toward highly variant concentrations
(shock loading). For this reason, research was conducted to identify, characterize,
and compare types of biological treatment processes and operational methods that suc-
cessfully handle problematic organic industrial waste. The objectives of the tech-
nology comparison are to identify the most robust biological treatment techniques
(applicable to the broadest range of waste classes) and to describe those treatment
characteristics that specifically enhance biodegradation of organic waste. Design,
performance, and economic comparisons of the studied biological treatment technologies
are presented to assist waste managers and engineers in the selection of proper treat-
ment methods. The treatment techniques studied were activated sludge, series lagoons,
deep shaft aeration, and pure oxygen biological systems.
17.
DESCRIPTORS
Biodeterioration
Waste treatment
Activated sludge process
Lagoons
Aeration
Organic wastes
Industrial wastes
KE1) WORDS AND DOCUMENT ANALYSIS
:\IDENTIFIERS/OPEN ENDED TERMS
Biological treatment
techniques
Organic industrial waste
Biodegradation technique
Deep shaft aeration
Pure oxygen biological
systems
COSATI l;icld/c;roup
13B
13. DISTRIBUTION STATEMENT
Release to public
19. SECURITY CLASS (This Report)
unclassified
21. NO. OF PAGES
377
20. SECURITY CLASS (Thispage)
unclassified
22. PRICE
EPA Form 2220-1 (9-73)
359
•fr U.S. GOVERNMENT PRINTING OFFICE: S1979-657-060/1623 Region No. 5-11
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