EPA-600/2-81-224
HEAVY METAL SOURCES AND FLOWS IN A MUNICIPAL SEWAGE SYSTEM
Literature Survey and Field Investigation
of the Kokotao, Indiana, Sewage System
by
K.J. Yost, R.F. Wukasch
T.G, Adams, Bert Michalczyk
Purdue University
West Lafayette, Indiana 47907
Grant No. R805631-01
Project Officer
S.A, Hannah
Wastewater Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
U.S. Environmental Protection Agency
Region 5, Library (5PL-16J
23,0 S. Dea?b0y« St-eet, Boooi 1670
CJaicago, IL 60604
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily reflect
the views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
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FOREWORD
The U.S. 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 testimonies to the deterioration of our natural
environment. The complexity of that environment and the interplay of its
components require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem
solution; it involves defining the problem, measuring its impact, and
searching for solutions. The Municipal Environmental Research Laboratory
develops new and improved technology and systems to prevent, treat, and manage
wastewater and solid and hazardous waste pollutant discharges from municipal
and community sources, to preserve and treat public drinking water supplies,
and to minimize the adverse economic, social, health, and aesthetic effects of
pollution. This publication is one of the products of that research and
provides a most vital communications link between the researcher and the user
community.
This report describes the flow of heavy metals (Cu, Ni , Cr, Cd, Zn, Pb)
and cyanide in the Kokomo, Indiana collection system and wastewafer treatment
plant. The primary objective is to determine the relative contributions of
domestic and non-domestic sources to the total pollutant load in the system,
and to assess the levels of discharge control required for the disposal of
municipal sludge by landfill or agricultural landspreading.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
ill
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ABSTRACT
The flow of heavy metals (Cu, Ni, Cr, Cd, Zn, Pb) and cyanide in the
Kokomo, Indiana collection system and wastewater treatment plant is analyzed.
The primary objective is to determine the relative contributions of domestic
and non-domestic sources to the total pollutant load in the system, and to
assess the levels of discharge control required for the disposal of municipal
sludge by landfill or agricultural landspreading. Sampling was conducted at
point source locations, in major sewer trunk- and feeder lines, and at the
treatment plant. Production and waste treatment data are presented for point
sources sampled for the purpose of characterizing metal and cyanide discharges
as a function of these parameters. A heavy metals mass balance is attempted
for the treatment plant. Metal removal factors are presented for various
plant operations.
A simple statistical approach is presented for the design of a cost-
effective sampling program for correlating point source and trunkline
pollutant sampling. The purpose is to minimize the amount of sampling
required to account for pollutants seen in trunkline and treatment plant
streams in terms of discharges from specific point sources.
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CONTENTS
Foreword iii
Abstract ..... iv
Figures vi
Tables ix
Acknowledgments ..,.. xiv
1. Introduction 1
2. Literature Review - . . . 2
Sources of heavy metals 2
Effects of heavy metals 8
3. Field Investigation of Heavy Metal Mass Flow in and Around the
Kokomo, Indiana, Sewage Treatment Plant .........._... 33
Introduction 33
Laboratory apparatus and procedures 38
Sampling program 45
Results 57
Conclusions 105
4. Sources and Flow of Heavy Metals and Cyanide in the Kokomo,
Indiana, Municipal Sewer System 114
Introduction . T .... 114
Methods and procedures 115
Point source testing 134
Collection system monitoring 156
Results and discussion 164
References 169
Appendices
A. Modifications of EPA Total Metals Methodology 176
B. Operational Settings for Perkin-Elmer Atomic Absorption
Spectrophotometers 180
C. Calculations to Determine Flow Rates of Three Select Streams
in the Kokomo, Indiana, Treatment Plant 182
D. Point Source Monitoring Tables 190
E. Trunkline Monitoring Tables 229
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FIGURES
Number
1. Approach used to determine sludge application rate and the
life of disposal site 27
2. Location of Kokomo, Indiana, sewage treatment plant 314
3. Plant layout 35
4, Process flow diagram 37
5. Effect of acid addition on metal concentration 40
6. Precision of nretal analyses 44
7. Mass balance diagram 46
8. Bottle used to sample primary influent 51
9. Plant personnel sampling route 58
10. Hydraulic balance 59
11. Cadmium profile 69
12. Chromium profile 70
13. Profile of copper concentrations in various treatment plant
streams 71
14. Nickel profile 72
15. Zinc profile 73
\
16. Iron profile 74
17. Lead profile 75
18. Cadmium mass balance. 86
19. Chromium mass balance 87
20. Copper mass balance ". 88
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21. Nickel mass balance 89
22. Zinc mass balance 90
23. Iron mass balance 91
24. Lead mass balance 92
25. Influent cadmium loading to plant during study . 95
26. Influent chromium loading to plant during study 96
27. Influent copper loading to plant during study ..... 97
28. Influent nickel loading to plant during study 98
29. Influent zinc loading to plant during study 99
30. Influent iron and lead loadingg to plant during study 100
31. Diurnal variation of influent Cd, Cu, and Ni . . . 102
32. Diurnal variation of influent Cr and Zn 103
33- Secondary effluent BOD- . 107
34. Effluent cadmium frequency distribution 108
35. Effluent chromium frequency distribution T". ... 109
36. Effluent copper frequency distribution , . 110
37. Effluent nickel frequency distribution . 111
38. Effluent zinc frequency distribution. . 112
39. Effluent iron and lead frequency distribution 113
40. A simplified drawing of the Kokomo sewer system with point
sources 116
41. A constructed Cipolletti weir ready for installation 119
42. A porcelain-covered steel staff gauge positioned upstream
and located so "0" on gauge corresponds to weir crest 120
43. A 24-hour mechanical clock to control the strip-chart flow
recorder 122
44. An ISCO automatic sequential sampler consisting of a 2-inch
by 2-inch board framework 123
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45. The construction of a Cipolletti weir 124
46. The installation of a Cipolletti weir 125
47. Treatment system for Point Source 2 137
48. Treatment system for Point Source 3 139
49. Treatment system for Point Source 4 142
50. Treatment system for Point Source 6 144
51. Treatment system for Point Source 9 148
52. Map of street surface sampling locations 152
vlii
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TABLES
Number Page
1. Metal Concentrations in Discharges from Selected Industries .... 3
2. Metals in Surface Runoff - Average Concentrations . . 4
3. Maximum Permissible Levels of Metal in Drinkinng Water. ...... 5
4. Metal Concentrations Found in Water Supplies of Mine Selected
Cities 6
5. Metal-Contain ing Consumer Products 7
6. Unpolluted Grcrundwater Metal Levels . . 8
7. Influent Metal Concentrations to Treatment Plants at Selected
Cities 9
8. Overall Metals Removal Efficiencies to Treatment Plants at
Selected Cities - 10
9. Calculated Effluent Metal Concentrations at Selected Cities .... 12
10. Sludge Metal Concentrations at Selected Cities 14
11. Heavy Metal Accumulation Factors in Sludges 16
12. Concentrations of Metal That Will Produce Significant
Reduction in Aerobic Treatment Efficiency 20
13. Significance of Heavy Metals Relative to Nitrification 23
14. Highest Continuous Dose of Metal That Will Allow Satisfactory
Anaerobic Digestion of Sludges 24
15. Concentrations of Soluble Heavy Metals Exhibiting 50 Percent
Inhibition of Anaerobic Digesters . 25
16. Effects of Heavy Metals on Aquatic Biota 29
17. Water Quality Criteria for Heavy Metals 30
18. Maximum Sludge Metal Applications for Privately Owned Farmland. . . 31
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19. Retention Times of the Various Process Tanks at Kokomo,
Indiana 33
20. Acid Addition Schedule Used to Investigate the Effects of
Delayed Acid Addition for Sample Preservation 39
21. Metal Concentration in Sequential Dilutions Used to
Standardize Instrument 42
22. Precision of Metal Analyses 43
23. Accuracy of Metal Analyses 45
24. Hydraulic and Metal Loading to Treatment Plant from Lone
Trunkline Mot Entering Through Plant Influent Manhole 49
25. Flow Calculation Formulas for Main Stream System 55
26. Flow Calculation Formulas for Sludge Stream System 56
27. Summary of Hydraulic Balances 60
28. Concentration of Heavy Metals Around the Entire Treatment
Plant 61
29. Concentration of Heavy Metals Around the Grit Chamber 62
30. Concentration of Heavy Metals Around Primaries * . . . 63
31. Concentration of Heavy Metals Around Aerators 64
32» Concentration of Heavy Metals Around Secondaries 64
33. Concentration of Heavy Metals Around Activated Sludge System. ... 65
34. Concentration of Heavy Metals Around Gravity Filters 66
35. Concentration of Heavy Metals Around Raw Sludge Holding Tank. ... 66
36. Concentration of Heavy Metals Around Zimpro Reactor 67
37- Concentration of Heavy Metals Around Zimpro Thickener 67
38. Concentration of Heavy Metals Around Vacuum Filters 68
39. Concentrations of Heavy Metals in Minor Plant Streams 68
40. Mass Balance Around the Plant as a Whole 79
41. Mass Balance Around the Grit Chamber 80
42. Mass Balance Around the Primaries 80
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43. Mass Balance Around the Aerators 81
44. Mass Balance Around the Secondary Clarifiers 81
45. Mass Balance Around the Gravity Filters 82
46. Mass Balance Around the Raw Sludge Holding Tank 82
47. Mass Balance Around the Zimpro Reactors 83
48. Mass Balance Around the Zimpro Thickeners 83
49. Mass Balance Around the Vacuum Filters. . ..... 84
50. Mass Balance Around Mixing Point 1 84
51. Mass Balance Around Mixing Point 2. .... ..... 85
52. Mass Balance Around Mixing Point 3« 85
53- Summary of Mas's Balances ...."... 93
54. Fraction of Influent Metal in the Sludge 93
55. Effects of Zimpro System and Vacuum Filters on Metal Loading
and Treatment Efficiency 104
56. Recovery of unknown Metal Samples Supplied by EPA . . . . T . » . . 127
57. Recovery of unknown Metal Samples Added to Sewage Prior to
Digestion and Concentration 128
58. Estimated Percent Standard Deviations at Nine Initial Metal
Concentrations for Replicate Sewage Samples Concentrated 40-
Fold During Digestion 129
59. Limit of Detectability for Heavy Metals 131
60. Metal Values for Analysis of Replicate Samples 131
61. Metal Concentrations from Analysis of Duplicate Samples ...... 132
62. Recovery of Cyanide as a Function of Initial Concentration
With Distillation Colorimetric Method 133
63- Precision of the Cyanide Distillation Colorimetric Method 133
64. List of Point Sources in Kokomo by Industrial Product or
Service 135
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65. Daily Discharges of Metal and Cyanide from Point Source 1
to New Pete's Run (T-3) Trunkline 136
66. Daily Discharges of Metal and Cyanide from Point -Source 2
to New-'Pete's Run (T-3) Trunkline 138
67. Daily Discharges of Metal and Cyanide from Point Source 3
to New Pete's Run (T-3) Trunkline 141
68. Daily Discharges of Metal and Cyanide from Point Source 4
to Washington Feeder (T-4a-2) and Subsequently to the
North Northside Interceptor (T-4a) 143
69. Daily Discharges of Metal and Cyanide from Point Source 5
to the Washington Feeder (T-4a-2) and the North Northside
Interceptor (T-4a) 143
70. Daily Discharges of Metal and Cyanide from Point Source 6
to Pete's Hun Interceptor (T-5a) 146
71. Daily Discharges of Metal and Cyanide from Point Source 7
to the Washington Feeder Line (T-4a-2) and the North
Northside Interceptor (T-4a) Trunkline 146
72. Daily Discharges of Metal and Cyanide from Point Source 8
to the Union Feeder Line (T-4b-1) and the South Northside
Interceptor (T-4b) Trunkline 146
73. Daily Discharges of Metal and Cyanide from Point Source 9
to Old Park Road Feeder Line (T-5b) and Pete's Run (T-a)
Trunkline 1*9
74. Concentrations of Influent and Effluent Waste Streams and
Removal Efficiencies for Point Source 9 Waste Treatment
System 1*9
75. Daily Discharges of Metals and Cyanide from Point Source 10
to Old Park Road Feeder Line (T-5b) and Pete's Run (T-5a)
Trunkline 150
76. Daily Discharges of Metal and Cyanide from Point Source 11
to the Apperson Feeder Line (T-4a-3) and the North Northside
Interceptor (T-4a) 150
77. Daily Discharges of Metal and Cyanide from Point Source 12
to the South Northside Interceptor (T-4b) Trunkline 151
78. Concentration of Heavy Metals in Kokomo Street Dust (Mean
and Standard Deviation, ug/g) 153
79. Loadings of Heavy Metals in Street Dust (Lbs and Lbs/Curb-
Mile)
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ACKNOWLEDGMENTS
Special recognition is due Mr. Shaun Sexton for directing the project
sampling effort, to Bert Michalczyk for treatment plant sampling and analysis,
and to Ted Adams for his laboratory analysis and data compilation efforts.
x±v
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80. Residential Inputs of Metal and Cyanide to Kokomo POTW . 157
81. Nonresidential Inputs of Metal and Cyanide to Kokomo POTW 158
82. Percent Input of Metals and Cyanide to Kokomo POTW from
Residential and Nonresidential Trunklines ....... 159
83. Daily Average Metal and Cyanide Flows in Three North
Northside Interceptor Feeder Lines. . . .... 159
84. Fractions of Wastewater, Metals and Cyanide Flows in North
Northside Interceptor Attributable to Appersonway,
Washington Street, and Indiana Street Feeders ..... 160
85. Random Superposition Flow Limits for Metals and Cyanide
In Combined Appersonway, Washington Street, and Indiana
Street Feeders 161
86. Fractions of Wastewater, Metals, and Cyanide Flows in New
Pete's Run Trunkline Attributable to Point Sources 1, 2,
and 3 - - ... 162
87. Random Superposition Flow Limits for Metals and Cyanide in
Combined Point Sources 1, 2, and 3 Effluent 162
88. Random Superposition Flow Limits for Metals and Cyanide in
Combined Point Sources 4, 5, and 7 Effluent 162
89. Random Superposition Flow Limits for Metals and Cyanide in"
Combined Point Sources 9 and 10 Effluent 163
90. Random Superposition Flow Limits for Metals and Cyanide in
Combined Point Sources 8 and 12 Effluent 163
91. Comparison of Metal Concentrations in Sludge Cake 165
xiii
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SECTION 1
INTRODUCTION
Municipal wastewater treatment removes particulate and soluble materials
from wastewater to the extent that discharge of this water to the natural
environment poses a minimal problem. The materials removed depend on
geographic location and characteristics of the population and industries
served by the system.
Traditionally, emphasis has been on removal and subsequent stabilization
of organic matter. Recently, interest has grown in the effects of other
pollutants on the environment. Notable among these are nitrogen, phosphorus,
heavy metals, and trace organics. The heavy metals are of concern owing to
their tcxicity. Unlike nitrogen or phosphorus, they are rarely concentrated
in toxic amounts in properly operating municipal treatment systems. The
stimulatory level of heavy metals is so low that the problem is one of
inhibition rather than stimulation. Also, heavy metals are conservative
pollutants, in that they are neither created nor destroyed. In a treatment
system, they must pass through in the effluent or be retained as residue.
Thus heavy metals are suited to long-term material balance studies around a
wastewater treatment plant. ""
The purpose of this investigation was to produce a comprehensive study of
the sources, flow, and effects of metals and cyanide in a municipal sewage
system. To achieve this goal, the research effort was divided into three main
segments: (1) A literature search to identify sources of metals to municipal
sewage treatment systems, the effects of metals on sewage treatment plants and
the environment, and existing or proposed legislation and guidelines for
controlling this problem; (2) a field study to investigate the heavy metal
mass flow pattern in and around the Kbkomo, Indiana, Sewage Treatment Plant,
and (3) a field study to monitor the sewer system of Kokomo, Indiana, for
heavy metals and cyanide sources and flow.
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SECTION 2
LITERATURE REVIEW
SOURCES OF HEAVY METALS
Metals that ultimately reach a sewage treatment plant originate from many
different sources. These sources can be categorized into five groups:
' industrial discharges
surface runoff
* domestic water supplies
domestic additions to the carriage water
' sewer infiltration
However, the relative importance of each category can vary greatly from city
to city.
Industrial Discharges
*
Industrial discharges are assumed to contribute the largest fraction of
total metal load to a municipal treatment plant. Wastewaters from the
following industries are usually the major industrial sources of heavy metals:
the primary metal.industries, fabricated metal products, machinery,
transportation equipment, chemicals and allied products, and leather and
leather products (Atkins and Hawley 1978). Of the fabricated metal
industries, electroplating generally contributes the most diverse types of
metals. Metal discharges from other industries have been analyzed by Klein
and others (1974), and are enumerated in Table 1. Other industrial sources of
heavy metal pollution include manufacturers of paper, linoleum, aniline dyes,
colored glass, paint, explosives, batteries, and rubber tires (Davis 1951).
Nickelcadmium battery manufacturing is also a pollutant contributor (McCaull
1971).
Surface Runoff
Surface runoff is a significant, and often overlooked^, source of metals
in the environment. Klein (1974) presented data on the average concentration
of metals in surface runoff, as have Wilber and Hunter (1975). The
concentrations given in these two sources differed, but were roughly of the
same order of magnitude, shown in Table 2. These differences are indicative
of many variables, most notably land use, the effectiveness of waste removal
from streets, the length of the antecedent dry period, and the intensity and
duration of the storm (Wilber and Hunter 1975). Wilber and Hunter's data are
based on an indepth study of two drainage areas and seven storm events, and
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TABLE 1. METAL CONCENTRATIONS IN DISCHARGES FROM SELECTED INDUSTRIES
(KLEIN ET AL. 1974)
Industry
Meat processing
Fat rendering
Fish processing
Bakery
Miscellaneous foods
Brewery
Soft drinks and
flavoring syrups
Ice cream
Textile dyeing
Fur dressing and
dyeing
Miscellaneous
chemicals
Laundry
Car wash
Cu
0.15
0.22
0.24
0.15
0.35
0.41
2.04
2.7
0.37
7.04
0.16
1.70
0. 18
Average
Cr
0.15
0.21
0.23
0.33
0.15
0.06
0. 18
0.05
0.82
20. 14
0.28
1.22
0.14
Concentrations
Ni Zn
0.07
0.28
0. 14
0.43
0.11
0.04
0.22
0.11
0.25
0.74
0. 10
0.10
0. 19
0.46
3.89
1.59
0.28
1.11
0.47
2.99
0.78
0.50
1.73
0.80
1.75
0.92
Cd
0.011
0.006
0.014
Q.QQ2
0.006
0.005
0.003
0.031
0.030
0.115
0.027
0.134
0.018
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Klein's data on grab samples collected at many different locations. Wilber
and Hunter conclude, that the time profile of the heavy metals in a storm sewer
after a rain is much like a unit hydrograph, that is, there is a pronounced
first-flush effect. Other significant conclusions are that the majority of
metals are associated with the particulate fraction of the solids which also
exhibited a first-flush effect, Eller (1976) confirms that the majority of
the metals is associated with the particulate fraction. Whipple and Hunter
(1977) give data about the loading of metal on land areas and conclude that
industrial land-use areas have more metal available to be washed into sewers
than commercial or residential areas. Shaheen (1975) meanwhile presents data
on the actual concentration of metal in street dust and concludes that, of the
metals studied, lead was present in the highest concentration (1.2 g/cc)
because of leaded fuel use. Shaheen proposes other sources of other metals:
motor oil (Zn), transmission fluid (Zn), antifreeze (Cu), undercoating (Ni,
Pb), rubber (?b, Cr, Cu, Ni , Zn), asphalt paving (Ni), brake linings (Cu, Ni ,
Cr), and concrete (Pb, Ni, Zn). Barkdoll, et al. (1977), qualitatively
substantiated these findings and also added atmospheric dustfall, accidental
spills, and antiskid compounds to the list.
TABLS 2. METALS IN SURFACE RUNOFF - AVERAGE CONCSNTRATIONS
Concentration (mg/1)
Metal Klein (1974) Wilber and Hunter (1975)
Cd
Cu
Cr
Ni
Zn
Pb
0.025
0.46
0.16
0. 15
T.60
0. 15
0.03
0.08
0.62
0.90
Bradford (1977), in a study to develop a predictive model for pollutant
loading from runoff in urban areas, presents data to sustantiate that heavy
metal loading relates to land use and traffic volume. Heavier industry and
increased traffic cause higher levels of heavy metals in solids collected from
the streets. Sartor and Boyd (1972) also found high levels of chromium,
copper, zinc, nickel, lead, and cadmium in street dust collected from nine
cities at an average total heavy metal load of 1.6 Ibs/curb mile.
Public Water Supply
Another source of heavy metals is the domestic household. These metals
originate from the metal present in the water supply and from metal added by
the consumer through the use of the water. The Environmental Protection
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Agency (EPA) has set maximum contaminant levels in drinking water for several
of the metals, shown in Table 3 (SPA 1976). These standards, which became
effective on June 24, 1977, superseded the Public Health Service Drinking
Water Standards of 1962, shown in parentheses in Table 3.
TABLE 3- MAXIMUM PERMISSIBLE LEVELS OF METAL IN DRINKING WATER
(EPA 1976)
MetalConcentration (mg/1)
Cd-
Cr
Pb
Zn
Cu
Ni:
0.010
0.050
0.050
No Standard
No Standard
No Standard
(0.010)
(0.050)
(0.050)
(5.00)
( 1 . 00 )
(No Standard)
The existence of these standards is evidence that heavy metals can and do
exist in municipal water supplies. Bartow and Weigle (1932) showed that many
ground- and surface-water supplies in Missouri, Kansas, and Oklahoma contain
up to 50 mg/1 of zinc. Later work by Barnet et al. (1969) showed'that the tap
water of Denver, Colorado, contained up to 22 ug/1 Cu, 100 yg/1 Fe, and 20
Ug/1 Zn. McCabe, et al. (1970), in a survey of water supplies in nine
metropolitan areas across the country, found concentrations of lead, copper,
cadmium,, and chromium above the then existing standards. Some of their data
are summarized in Table 4. Klein et al. (1974) estimated that the water
supply contributed 20 percent of the copper and 7 percent of the zinc which
entered the wastewater treatment plants. For Klein's data, this is equivalent
to 0.061 mg/1 Cu and 0.032 mg/1 Zn in the water supply. The copper source is
usually copper sulfate which is added to reservoirs to control algal growth.
Finally, Newell (1971) labels hydrofluosilicic acid (used as an agent in
providing fluoride) as a possible, but very minor, lead source.
Consumer Products
Domestic water use adds to metals in the water supply by solution of
water pipes, now primarily copper and brass or formerly lead, or by direct
addition through use of household products containing metals. Epstein (1974)
identifies some cosmetic products which contain metals. These include such
things as shaving creams (Zn), hair dyes (lead acetates), and dandruff
shampoos (Zn). McCaull (1971) also points to phosphate detergents (and to
fertilizers) as a source of metal, particularly cadmium because of the
ultimate source of the phosphate in deposits of fossilized marine life which
were rich in cadmium (notably fish teeth). McCaull labels black polyethylene
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water pipes as a possible cadmium source. A very comprehensive study (Atkins
and Hawley 1978) enumerate household products which contain metals. This
compilation includes, but is not limited to, cadmium, chromium, copper, iron,
nickel, lead, and zinc. A very small portion of this material is shown in
Table 5.
TABLE 4. METAL CONCENTRATIONS FOUND IN WATER SUPPLIES OF NINE SELECTED
CITIES (MCCABE ET AL. 1970)
Metal
Highest
Concentration
Found (mg/1)
Number of Cities
Where Drinking
Water Standard
was Exceeded
Percentage of
Cities Sampled
Whose Water
Violated Standards
Pb
Cu
Cd
Cr
0.64
8.35
3.94
0/079
37
42
4
5
1.4
1.6
0.2
0.2 "-
Infiltration
Infiltration of groundwater to the system is the final source of metal to
the sewer system. Newell (1971) found copper and lead at O.on and 0.0085
mg/1, respectively, in groundwwater in New England, proving that unpolluted
groundwater can have heavy metals. A study by the U.S. Geological Survey
(1972), which collected samples from 98 locations in a 120,000-square-mile
area in Washington, Oregon, and Idaho, found copper, chromium, nickel, and
lead at the concentrations shown in Table 6. However, in an urban
environment, groundwater can become polluted with heavy metals, as shown by
LLeber and Welsch (1954) and Davis (1951). These studies both centered on the
Long Island area of New York and dealt with cadmium and chromium pollution of
groundwater from industrial sources.
Klein, et al. (1974), were the only researchers who attempted to quantify
the sources of metals to a treatment plant. They concluded that residential
and industrial sources were major contributors and were about equal in
magnitude. From the other studies, it is clear that these results cannot be
extrapolated to other locations but must be arrived at on a case-by-case
basis. This type of study should include a measurement, or at least an
estimation, of the metal loads associated with the five direct sources
discussed here. Only in this way can a true picture be presented for a given
location.
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TABLE 5. METAL-CONTAIJfING CONSUMER PRODUCTS
Metal
Product
Compound
Cadmium
Chromium
Copper
Nickel
Zinc
Lead
Iron
Shampoo
Dyes, tints-hair
Lawn Pesticides
Metal Cleaners
Caulking Compounds
Paint
Dyes, tints-hair
Skin Ointment
Foot -Powder
Hemorrhoid Treatments
Antacid
Dyes, tints-hair
Paint
Floor Cleaners
Toilet Bowl Cleaners
Skin Cream
Spray Deodorant
Mouthwash
Shampoo
Paint
Roach Killer
Dyes, tints-hair
Face Powder
Dyes, tints-hair
Mascara
Eyebrow Pencil
Cadmium laurate
Cadmium stearate
Cadmium chloride
Cadmium succinate
Chromic acid
Chromium
Many compounds depending on color
Cupric chloride
Copper capryolate
Copper salts
Copper sulfate
Cupric phenolsulfonate
Nickel
Nickel oxide (yellow and brown)
Zinc stearate ""
Zinc chloride
Zinc oxides
Zinc phenolsulfonate
Zinc oxide
Zinc pyrithione
Depends on color
Lead arsenate
Lead acetate
Iron oxide
Ferric chloride
Ferrous sulfate
Iron oxide
Iron oxide
7
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TABLE 6. UNPOLLUTED GROUNDWATZR METAL CONCENTRATIONS (NEWCOMB 1972)
Concentration (rag/1)
Metal Max. Min.
Cr
Pb
Cu
Ni
0.03
0.022
0.03
0.13
0.002
0.001
0.004
0.004
EFFECTS OF HEAVY METALS
Heavy metals have three effects on a municipal sewage treatment plant.
The primary effect is on the process itself, that is, the inhibitory effect of
heavy metals to anaerobic or aerobic biological processes. Second, the effect
on the sludge produced is of concern. This effect manifests itself in the
method used for ultimate disposal, which might be limited by a high metal
concentration. Finally, the effects of heavy metals on the aquatic organisms
and downstream users must be considered.
Metal Effects at Waste Treatment Plants
Concentrations "
The sources of heavy metals can contribute enough that a fairly high
concentration enters the treatment plant. Typical influent concentrations are
abundant in the literature, and Table 7 summarizes some of these data. These
concentrations vary somewhat from city to city, but for a given metal are of
roughly the same order of magnitude. For example, iron generally is present
at a concentration greater than 1 mg/1, whereas the concentration of cadmium
is only rarely greater than 0.050 mg/1.
Table 8 summarizes removal efficiencies at the plants shown in Table 7.
It is obvious that there is a wide range in removal efficiencies at different
plants. Cadmium is reported to be removed between 0 to 80 percent, chromium
13 to 88 percent, copper 13 to 86 percent, nickel 0 to 53 percent, zinc 41.3
to 75 percent, iron 47 to 85 percent, and lead 0 to 92 percent. Obviously
there is no universal removal efficiency for a given metal.
Because of the variable influent concentration and the widely variable
removal efficiency, there is a wide range in the concentration of metals in
the effluent. These are calculated from the data in Tables 7 and 8 and are
presented in Table 9. Here, again, there is no universal metal concentration
in a treatment plant effluent.
-------
TABLE 7. INFLUENT METAL CONCENTRATIONS TO TREATMENT PLANTS AT SELECTED CITIES
City
Anderson, Ind.
Buffalo, NY
Dayton, Ohio
Grand Rapids,
Michigan
Muddy Creek,
Ohio
Muncie, Ind.
Pittsburg,
Pennsylvania
Wahiawa,
Hawa i 1
Winnipeg, Mon.
Avg. of 6 Cities
Near Kansas City
Burlington, Ont.
Survey of 20
Plants in Ont.
Cd
9.5
18
27
8
21
5-65
20.2
6
20
Cr
1180
208
400
240
95
12-18
166
220
290
970
Cu
2820
137
500
260
127
62-90
210
146
310
\
300
N1
(ng/D
2790
50
500
140
78
60-70
32
330
110
Zn Fe
1500
337
* i _ _
1200
1150
648
1000-
200-320 1180
329
733
2400 1540
'1120 6580
Pb
160
99
930
119
40-70
117
210
230
170
-------
TABLE 8. OVERALL METALS REMOVAL EFFICIENCIES TO TREATMENT PLANTS AT SELECTED CITIES
City
Anderson,
Indiana
Buffalo,
New York
Dayton ,
Ohio
Grand Rapids,
Michigan
Muddy Creek,
Ohio
Munde,
Indiana
Pittsburgh,
Pennsylvania
Wahlawa,
Hawaii
Winnipeg,
Mon.
Avg. of 6 Cities
M i-\ a w-» I/ a fi C1 a c f "I "i* \t
Near Kansas i/ity
Burlington,
Ontario
Treatment
Received
Secondary
Treatment
Secondary
Treatment
Trickling
Filters
Secondary
Treatment
Conventional
Act. SI.
Secondary
Treatment
Secondary
Treatment
Step
Aeration
Pure
Oxygen
Conventional
Act. SI.
Removal Efficiency (%)
Cd Cr Cu N1 Zn
59 88 86 41 75
37.7 62,2 61.0 11.0 41.3
A(\ 7 _
*tu, /
19-66 13-57 18-41 35-51
62.5
78 68 0 70
67 67 56 10 65
59 32 74 42 71
68 77 0 80
\
ic 07 AQ ' A7
ID J/ t3 HI
80 79 73 16 77
'
Fe Pb
- 75
73.8
-- 82
- 81
85 73
49
49
*t-J
73 93
-------
TABLE 8, CONTINUED
dty
Treatment
Received
Cd
Removal Efficiency (%)
Cr Cu Ni Zn Fe
Pb
4 Ontario
Cities
5 Ontario
Cities
11 Ontario
Cities
Lagoon
Systems
Primary
Treatment
Activated
Sludge
0 13
13 69
28 76
13
30
80
40
-21
53
42
42
67
70 0
47 48
79 70
-------
TABLE 9. CALCULATED EFFLUENT METAL CONCENTRATIONS AT SELECTED CITIES
City Cd
Anderson,
Indiana 3.9
Buffalo,
New York 11.2
Dayton ,
Ohio 16
Grand Rapids,
Michigan
Muddy Creek,
Ohio 3
Muncie,
Indiana
Pittsburgh,
Pennsylvania 7
Wahiawa,
Hawaii 2-27
Winnipeg,
Mon.
Burlington,
Ontario 1
Los Angeles 50
Cr
142
78.6
136-325
53
31
8-12
53
61
290
Effluent
Cu
395
53,4
215-435
83
56
16-23
48
\
84
320
Concentration
N1
885
44.5
295-410
140
70
35-41
32
277
280
(pg/D
Zn Fe Pb
375 40
'704 25.9
588-780
345 167
227 23
53-93 150-177 11-19
66 60
552 416 16
460 700 60
-------
The above conclusions of no universal value can be drawn for the sludge
from data presented in Table 10 illustrating this point. The data are drawn
from somewhat different cities than those in Tables 7 through 9. In the
literature, there is no consistent basis for expresssing the metal content of
the sludges and it is not possible to covert these data to a common basis.
Also, the sludges arise from different points in a treatment plant, such as
from the waste activated or the final filter cake, thus making comparison
meaningless.
Olthof (1978) summarizes some of the above data and calculates an
"Accumulation Factor." This is simply the ratio of total metal concentration
in the sludge (on a mg/kg dry weight basis) to the total concentration (mg/1)
of metal' removed from the influent. His data show that the accumulation
factor of most sludges is about 10,000 and even suggests that this value may
be used in design when better data are unavailable. His values are shown in
Table 11.
Removal Mechanisms
The great variability in reported metal concentrations indicates that
there is no simple single removal mechanism for heavy metals and that
different waste treatment plants will experience different degrees of toxicity
to biological treatment systems, depending on the heavy metal values at a
particular site. Therefore, the literatue was searched as it pertains to
heavy metal removal mechanisms and the toxicity of heavy metals.
The mechanisms of heavy metal removal seem to be the subject of much
debate. This topic is clouded by the types of studies undertaken to quantify
heavy metal removal. For example, some authors use bench-scale (Cheng,
Patterson, and Minear 1975; Neufeld and Hermann 1973) systems with synthetic
feed, others use pilot plants (Moore 1961; McDermott et al. 1963, 1962, 1965),
while still others attempt to analyze data from existing treatment plants
(Nomura and Young 1974; Brown and Hensley 1973; Oliver and Cosgrove 1974).
Accordingly, some studies incorporated the effect of primary sedimentation
while others did not. The incomplete data often reported further obscures
analysis, that is, insoluble versus dissolved metal, or the solids
concentration in the influent, effluent, or in-process streams. However,
three predominant removal mechanisms emerge from the literature-:
precipitation, flow adsorption (enmeshment and adsorption), and ion exchange
on metal oxides (most notably oxides of iron).
In primary treatment, settling of insoluble metals or metals absorbed to
particulates is the most generally accepted removal mechanism (Nomura and
Young 1974). Brown and Hensley (1973), in a study of primary treatment
plants, found that as suspended solids removal increases, so does heavy metal
removal. Their work also indicates that secondary plants which have better
suspended solids removal experience increasing heavy metal removal, which
asymptotically approaches complete metal removal. This points to the removal
of soluble metal in addition to particulate metal in a secondary plant. In a
series of articles, Stones (1955, 1958, 1959a, 1959b) investigated, in
addition to other work, the removal of metals by sedimentation. He found that
chromium, copper, nickel, and zinc are removed at 28 percent, 45 percent, 27
percent, and 41 percent efficiency, respectively.
13
-------
TABLE 10. SLUDGE METAL CONCENTRATIONS AT SELECTED CITIES
City
Bryan,
Ohio
Buffalo,
New York
Burlington,
Ontario
Grand Rapids,
Michigan
Richmond,
Indiana
Rockford,
Illinois
Toledo,
Ohio
Wahiawa,
Hawaii
Winnipeg,
Mon.
Unidentified
Descriptor
Digested
SI. (mg/1)
Waste Act.
(mg/kg Dry)
Digested St.
(mg/kg Dry)
Digested
(mg/1)
Digested SI.
(mg/1)
Digested SI.
Sludge Cake
(mg/kg Dry)
Digested SI.
(mg/1)
Digested SI.
(mg/1)
Trickling
Filter SI.
(mg/kg DWB)
Cd Cr
___
100 2540
2.1 127
2700
95
358
21 1170
1.95 0.71
- 2200
\
250
Metal Concentration
Cu Ni Zn Fe Pb
27
1570
159
2500
88
105
440
9.50
522
330
2
315
39
1700
4
28
320
1.02
64
50
220
2275 1800
1205 471 90
5700
73
390
2580 90000 630
36 350 3.70
2500 675
970 27900 70
-------
TABLE 10, CONTINUED
City
Descriptor
Cd
Cr
Metal Concentration
Cu Ni Zn
Fe
Pb
6 Cities
Unidentified
8 Indiana
Cities
Avg. 150
Plants in U.S.
(mg/kg)
6-135 116-788 229-1849
745-
15270
Final Sludge
(rog/kg DWB) 16-846
Aerobic
(mg/kg DWB)
135 1270
_, 6 Ontario
01 Cities
1553-
662-8381 80--3184 20119
Anaerobic
(mg/kg DWB) 106 2070 1420
940
Waste Act. SI.
(mg/kg DWB) 0.36 87 31
324-2595
545-7431
400 3380 16000 1640
150 2170 11000 720
6.6 103 534 19
-------
TABLS 11. HEAVY METAL ACCUMULATION FACTORS IM SLUDGE
Accumulation
City Type of Sludge Factor*
Muncie, Indiana Digested Secondary 9QOQ
Grand Rapids,
Michigan Digested Secondary 17800
Sioux City, -Iowa Digested Primary 9520
Bryan, Ohio Digested Secondary 7400
Richmond, Indiana Digested Secondary 16000
Rockford, Illinois Digested Secondary 8500
Shelby, Ohio Raw Secondary 11000
* Ratio of metal concentration in sludge to that in plant
influent.
This action was found to be nonbiological in origin since similar results
were arrived at with sterilized as well as raw sewage. However, this does not
eliminate the possibility that metals do not adsorb onto settleable biological
material. Oliver and. Cosgrove (1974) indicate that less than 1 percent of
dissolved metals, with the exception of chromium and iron, are removed by
primary sedimentation, and when a slug of metal enters a plant, the dissolved
fraction passes unchanged through the primaries. Jenkins et al. (1964) showed
that contact of a heavy metal solution containing copper, chromium, nickel,
and zinc with domestic sewage caused precipitation of the metal hydroxides.
It should be noted that very high metal concentrations were studied (up to 100
mg/1) and that background metal concentrations existed up to 2.43 mg/1. Chen,
et al. (1974), in studies investigating the size distribution of heavy metals,
have shown that only 20 to 40 percent of the total metals in the primary
effluent are dissolved. Nickel and lead are exceptions because greater than
80 percent are dissolved. While this indicates that the removal mechanism is
sedimentation, it does not confirm this because no data on the size
distribution of metals in the raw sewage were presented to show that the
percent of dissolved metals increased through primary sedimentation. However,
Oliver and Cosgrove (1974) do state that "for most metals, the proportion of
dissolved to total metal increases as they pass through the system," and the
data of Chen, et al., show this effect. The above studies all point to
precipitation and sedimentation of metal-adsorbing particles as the removal
mechanism active in primary treatment.
Within the biological treatment system, particularly activated sludge,
all three mechanisms operate to remove heavy metals, that is, precipitation,
16
-------
floe adsorption, and adsorption-ion exchange on metal oxides. The most widely
recognized and most studied mechanism is floe adsorption. Freedman and Dugan
(1963) have shown that the bacterium Zpogloea has the ability to uptake and
concentrate heavy metal ions beyond those which are needed for use as enzyme
cofactors within the cells. The authors demonstrated that the uptake of metal
increases because of net increase in cell-floe weight rather than cell
numbers, since under varying environmental conditions the cell floe weight is
often not proportional to cell numbers. This essentially is the justification
for others' work where metal uptake is related to mixed-liquor-suspended
solids rather than cell counts. Cheng, et al. (1975), and Neufeld and Herman
(1975), in batch-type fill and draw-reactors, both show that the uptake of
heavy metal by the biological floe is essentially an instantaneous phenomenon
and the rate is relatively independent of metal species or concentration.
Salotto (1964) studied the relationship between organic loading on'toxicity of
copper to the activated sludge process, and concluded that organic loading did
not markedly affect the toxicity of copper but that under conditions of higher
loading, and higher effluent COD, there was less metal removal. Also, Cheng,
et al. (1975), and Patterson (1978) both showed that the uptake of heavy
metals was dependent upon the mixed-liquor-suspended solids concentration as
well as the pH. These facts all point to adsorption as a possible removal
mechanism.
Cheng, et al. (1975), and Patterson (1978) theorize that ion-exchange can
explain the above facts. They develop very similar models (essentially only
the notation is different) to simulate this phenomenon. It is based on the
fact that the metal bound per unit weight of ion exchange medium to the metal
in solution is a constant at equilibrium. In a system in which complexing
ligands are also present, there will be competition between the ligands and
the ion-exchange-media for the metal ions. The equilibrium concentrations
will be determined by the relative magnitude of the stability constants for
the metal-ligand and metal-exchange media complex. The stability constant is
essentially an equilibrium constant for the reaction between a soluble metal
and the ligand or exchange media. Theoretically, activities rather than
concentrations should be used because of the surface chemistry involved.
In an activated sludge system, the exchange media is the mixed-liquor-
suspended solids and the ligands are the soluble COD or TOC. Stability
constants based on these gross parameters have been termed conditional
stability constants by Patterson. This system qualitatively explains the fact
that effluent metal increases with increasing effluent COD (or BOD) (Patterson
1978). Cheng, et al~(1975), experimentally determined stability constants
for nickel, while Patterson (1978) did so for copper. It should also be noted
that the constants are a function of pH because of the competing reactions
involving the hydrogen ion at the binding sites, and that as the pH increases
(and [H+] decreases), the stability constant increases. This implies better
removal of heavy metals at higher pfi values.
Neufeld (1977) approaches the phenomenon of heavy metal uptake by
activated sludge as an adsorption phenomenon, and chooses the liquid-phase
metal concentration and the quantitty of metal associated with the biomass (mg
metal/g biomass) as the important variables. He postulates that the reaction
rate depends upon the liquid phase metal concentration to some power and the
17
-------
degree of saturation of the biomass with metal raised to a different power.
This amounts to the difference of rate expressions for the given forward and
reverse reactions. At equilibrium, the rate will be equal to zero and thus
the liquid phase concentration can be related to the concentration associated
with the biomass. If the two exponents in the rate expression are numerically
equal, the expression reduces to the equation of the Langmuir isotherm, and
the constants can be evaluated as such. In general, it was found that the
exponents were not equal and a more involved method must be used. Neufeld
quantitatively evaluates the model for several metals. The results show the
low affinity characteristic of nickel and the high affinity for lead.
The activated sludge system removes inert and biodegradable solids (Grady
and Lin 1977) and can thus remove metal -that is in a suspended form. This
applies whether the metal enters the aerators as carry-over suspended solids
from the primary, or is precipitated in the aerator because of the changed
chemical environment. The accepted mechanism of removal is floe enmeshment of
the solid material.
The tendency for a metal to precipitate in an aeration basin is dependent
upon many parameters, such as pH, oxidation-reduction potential, and the
dissolved anions which are present (Hem 1963). Within an aeration .basin, the
pH is usually near the neutral range, while metal hydroxides have "a minimum
solubility at higher pH values (Sawyer and McCarty 1967). This alone does not
determine whether the metal is soluble or not, because the value of the
minimum solubility changes drastically for different oxidation states of a
given metal, as well as ligand effects. The oxidation state of a given metal
in solution is dependent primarily on the oxidation-reduction potential. (The
presence of carbonates, sulfates, chlorides, etc.r can alter the behavior of a
pure metal. Water system and quantitative theoretical predictions about heavy
metal precipitates in an activated sludge system are difficult to make.)
However, one of the interesting primary metals of the seven to be studied is
iron because of its displayed tendency to be oxidized to the ferric state and
precipitated as a hydroxide or oxide within the pH or ORP ranges of an
aeration basin (Pourbaix 1966) (neutral to alkaline pH and -43 to +160 mv ORP
(Backmeyer and Drautz 1961)). Thus the activated sludge system will
concentrate this iron precipitate in the secondary settler.
An iron oxide of hydroxide precipitate can help heavy metal removal
through the activated sludge process. This fact was noted during studies in
which ferric chloride was being evaluated for phosphorus removal at Grand
Rapids, Michigan (Green et al. 1973). This study showed enhanced heavy metal
removal when iron was added to the aerators. Stumm (1967) has noted that the
hydrous metal oxides show a strong tendency to interact with cations and
anions in solution, depending on the pH and isoelectric point. When the metal
oxide is positively charged, anion exchange occurs, and when it is negatively
charged (i.e., at a pH greater than the isoelectric point), cation exchange is
predominant. Similarly, Jenne (1968) has noted that hydrous oxides of iron
and manganese act as a medium which adsorbs heavy metals in soil and water
systems. Also, pH and Eh (oxidation reduction potential) are the most
significant variables, but organic chelates, the concentration of a particular
metal, and the concentrations of competing metals influence the degree of
uptake. Posselt and Weber (1974) modeled cadmium uptake by hydrous metal
18
-------
oxides of iron and manganese and found that it could be fit to a Langmuir
isotherm equation. They also noted that the limiting sorption capacity and
sorption affinity tend to increase as pH is increased beyond the zeta
potential. This is in qualitative agreement with the work of Stumm and Jenne.
In summary, there are three removal mechanisms active during biological
treatment. The major and most widely recognized is adsorption onto the
biological flow. A second is carry-over of insoluble metal which is removed
by floe enmeshment. The last is the sorption of trace amounts of metal on
hydrous metal oxides, particularly iron. All three mechanisms depend upon
secondary sedimentation to ultimately remove the metal-laden suspended solids.
There is little information regarding removal of heavy metals through a
gravity filter. Oliver and Cosgrove (197*0 believe that in order for a
tertiary treatment process to achieve a high degree of heavy metal removal, it
must be aimed at removing the dissolved metals. Data presented by Argaman and
Weddle (1973) indicate removal efficiencies on the order of 0 to 60 percent
for filters, however, the data are taken from filters operating at physical-
chemical pilot plants. It would be reasonable to assume that the maximum
degree of metal removal in a filter would occur when all suspended matter is
removed, leaving only the dissolved metal.
Toxicity
The potential of heavy metal as a toxicant of aerobic organisms has been
known for some time. Jenkins and Hewitt (1942) studied the toxic effects of
chromium on trickling filters and activated sludge. Edwards and Nussberger
(194?) indicated chromium as the cause of a treatment plant upset at Tallmans
Island. Coburn, in 1949, noted that excessive copper, zinc, and iron have
caused problems at the Fostoria, Ohio, treatment plant. However, these and
many similar ones of the same period had just begun to investigate the subject
of heavy metal toxicity and were often qualitative in nature.
The problems of toxicity studies with a diversity of life forms are
discussed by Barth. He points out that life has been obvserved in many
environments encompassing temperatures of -18°C to 104°C, pH of 0 to 13.
pressures of 0 to 1,400 atm, and Eh potentials of -500 to -t-500 mv. Therefore,
in any toxicity study on mixed cultures, there can be organisms which survive
even the most severe conditions. Ingols and Fetner (1961) show that two
species of bacteria respond in very different ways to the same environmental
stress, in this case, a high chromium concentration. Thus the effect of the
toxicant is not as clear-cut as stimulation, inhibition, and death when
studying a single organism, but is manifested in a modified reaction of the
culture as a whole to a given stress.
The various authors in the field have not chosen a consistent measure of
toxicity, and as a consequence results are often difficult to compare. For
example, one author may use effluent quality and another oxygen uptake as
parameters. Barth (n.d.) also points out that, in general, aerobic systems,
because of the diversity of species present, will respond to a toxicant by
being only slightly inhibited at a low level of toxicant and then reaching a
plateau of relative insensitivity before total failure at a high
concentration. In contrast, because of their limited species diversity,
19
-------
anaerobic systems will often fail suddenly and completely as a given
concentration of toxicant is exceeded. This effect has been observed in the
literature.
In the early 1960s, a series of studies was conduted by the Robert A.
Taft Sanitary Engineering Center (1965) in Cincinnati to investigate the
toxicity of heavy metals to biological treatment processes (Moore 1961;
McDermott 1963, 1962, 1965; Salotto 1964; English 1964; Barth 1964).
Chromium, copper, zinc, and nickel were studied in pilot-scale, activated
sludge systems with primary settlers. The investigators used effluent COD,
BOD, and turbidity as the measure of toxicity, that is, an increase in these
criteria was assumed to be a result of the toxic effect of the heavy metal.
Table 12 (Taft 1965) presents the level of metals that gave a statistically
significant increase in COD, BOD, or turbidity measurements. The studies also
showed that the activated sludge system could withstand a total heavy-metal
concentration of up to 10 mg/1, either singly or in combination, as long as
the toxic levels of any particular metal are not exceeded, with about a 5
percent decrease in organic removal efficiency.
TABLE 12. CONCENTRATIONS OF METAL THAT WILL
PRODUCE SIGNIFICANT REDUCTION IN
AEROBIC TREATMENT EFFICIENCY
Metal
Cr
Cu
Ni
Zn
Continuous Dose
mg/1
10
1
1-2.5
5-10
Slug Dose
mg/1
>50Q
>75, <160
>50, <200
160
Slug doses of four-hour duration were also studied for each of the four
metals. A slug of 100 mg/1 of chromium caused a slight decline in BOD removal
efficiency for about 20 hours, followed by full recovery. Slug doses of
copper in concentrations greater than 50 mg/1 caused severe impairment of
plant operation, with recovery only after about 100 hours. Zinc and nickel in
slug doses of 160 mg/1 and 200 mg/1, respectively, caused serious reductions
in treatment plant efficiency, followed by recovery after 40 hours for both
metals. In one of the studies (English 1964), an intentional slug dose of
chromium was fed to a 0.8 MGD activated sludge plant in Bryan, Ohio. The slug
consisted of 150 gallons of chromic acid anodizing solution fed into the
municipal sewer system. At the peak of the slug, the sewage had a
concentration of 500 mg/1 chromium and a pHof 5-7. Ninety-five percent of
the metal was removed by the system, with no long-term adverse effects. No
deterioration of treatment plant parameters was noted, with the exception of
an increase in suspended solids for a short period after receiving the slug.
20
-------
One of the studies was aimed at substantiating the pilot-scale results by
monitoring four municipal treatment plants receiving metallic wastes. These
plants receive the metallic constituents on a continuous basis with frequent
slug doses. The results indicate that in the range of 1 to 9 mg/1 of heavy
metals there is-no serious reduction in treatment plant efficiency.
Jenkins and Hewitt (19^2) were the first to allude to the fact that the
concentration of metal alone is not the only factor determining toxicity.
They noted that a given concentration of metal had a greater effect on an
activated sludge system than on a trickling filter, and concluded that it was
because of the more concentrated microbial phase in the trickling filter.
Ayers (1965) concluded that toxicity of copper, and by extension the other
heavy metals, is affected by the sewage strength, as well as by mixed liquor
and copper concentrations. This is best explained by considering the work of
Cheng, et al. (1975), and Patterson (1978) concerning the effect of chelating
agents on effluent metal concentration, as discussed previously. Directo
(1962) also noted the relationship between influent metal concentration,
influent COD, aerator-suspended solids, and effluent COD, and showed that
higher suspended solids, lower influent metal concentration, and lower feed
COD all result in less toxicity, as measured by effluent COD increase. Dugan
(1975) has shown that, when a polymer matrix surrounds a cell, the metal ions.
accumulate with the polymer and do not reach the cell membrane surface. This,
in part, explains the high tolerance of such cells for ions that are normally
toxic.
Hartmann (1968) first attempted to characterize the type of inhibition
caused by heavy metals according to the Michales-Menton scheme of enzyme
kinetics. The conclusion was that different metals exhibited different types
of toxicity, i.e.r either competitive, uncompetitive, or noncompetitive,
depending upon whether the slope, vertical intercept, or both of the
Lineweaver-Burke plots are functions of the inhibitor concentration.
Discussions of this article by Patterson and Brezonik (1969) and Banerji
(1979) clarify some of the points made by the original authors.
Neufeld and Hermann (1975) expanded the original studies of Hartmann
(1968) with the aim of using the modified Michales-Menton kinetics for design.
Michales-Menton kinetics relate the specific growth rate to the substrate
concentration by the following relationship:
. V
These are slightly different than the nomenclature of the Monod relationship
commonly used, but the concepts are equivalent. In this case:
V s forward reaction rate; measured as grams of
volatile suspended solids produced per mg of
chemical oxygen demand satisfied per minute
(gVSS/mg02/min)
21
-------
VM = maximum forward reaction rate obtained at
high substrate concentrations
KM = the substrate concentration which corresponds
to one-half of the maximum forward reaction
rate; measured as mg chemical oxygen demand
per liter (mg COD/1)
F s substrate concentration; measured as mg
COD/1 .
The resulting concentration of organisms measured as volatile suspended solids
can be related to the mean cell residence time and hydraulic residence time
by:
xa
boc
where FQ s feed concentration (mg COD/1)
9 = hydraulic" residence time (day)
X = volatile suspended solids concentration (mg/1)
YQ s- true growth yield; mg of VSS produced
b s specific decay rate in mg VSS decayed per
mg VSS present per day (day ~^) *"
The author determined the constants V^, KM, YQ, and b as functions of the
metal to suspended solids ratio. Results were presented for mercury, cadmium,
and zinc. These values, were then used to compute predicted effluent COD as a
function of sludge age with metal concentration as a parameter. No metal
interactions were studied, as only one metal at a time was considered.
Heclc, et al. (1972), refuted the conclusions of Hartmann (1968) and
Neufeld and Hermann (1975) and concluded that the inhibition is independent of
effluent substrate concentration. However, he was working with glucose, which
has a very low KM, and therefore he could not have investigated the very low
substrate concentrations necessary to show Michales-Menton kinetics. He also
concluded that total metal controlled the log growth rate. An analysis of the
data shows this conclusion was reached because at hiigher soluble copper
concentrations, there was no change in the rate constant for substrate
removal. However, there was an increase in effluent COD and thus in organic
chelating compounds which would make the soluble copper increase but would not
affect the available or free copper. He did show that the initial lag period
(and hence acclimation time) was a function of the metal concentration.
Malaney, et al. (1959), also noted that the lag period was a function of the
metal concentration.
22
-------
Poon and Bhayani (1971) investigated the toxic effects of metals on two
bacteria, Zooglea ramigera and Geotrichum eandidum, using Michales-Menton
models. They concluded that the toxic behavior of metals varies with the
biological species present. However, as was pointed out by Chaudhuri and
Engelbrecht (197O, these studies were done on pure cultures using a simple
substrate, and any extrapolation to mixed cultures on a complex substrate is
risky.
Edwards and Nussberger (194?) noted the disappearance of Sphaerotilus
when chromium was present in high concentrations, as did Moore, et al. (1961).
Neufeld (1940) showed that excess heavy metals could cause "deflocculation" of
activated sludge. However, this is different from bulking sludge where many
filamentous organisms are present. Deflocculation is characterized by fine,
stabilized pinpoint floe in the overflow of secondary clarifiers. Thus this
work does not contradict previous studies.
Heavy metals exert a toxic effect on the nitrifying organisms,
Nitrosomonas and Nitrobacter, independent of the effects on carbon-removing
organisms. This was noted by Jenkins in 1942, by Moore, et al. (1961), and by
Edwards and Nussberger (1947) for chromium. It has been reported that
nitrification is inhibited at the concentration shown in Table 13 (Roper 1977;
Water Pollution Control Federation 1977). These levels are much lower than
those for BOD removal, and substantiate the premise of Barth presented
earlier.
TABLE 13. SIGNIFICANCE OF HEAVY METALS
RELATIVE. TO NITRIFICATION
(ROPER 1977; NEUFELD 1976)
Concentration at Which
Metal . Inhibition Occurs (mg/1)
Single Stage Two Stage
Nitrification Nitrification
Zinc
Lead
Chromium
Copper
Cadmium
Nickel
0.08-0.50
Q.50
0.25
0.005-0.5
0.25
0.3-2.0
2.0
1.9
0.33-3.33
0.42
There is little in the literature about heavy metal inhibition of
trickling filter operations. While Stones (1955, 1958, 1959a, 1959b) shows
23
-------
that trickling filters can remove heavy metals, no mention was made on the
effect of those metals on the organisms present. Jenkins and Hewitt (1942)
show that 1 mg/1 chromium has no effect on nitrification of removal of organic
matter. However, 10 mg/1 causes a reduction in the concentration of nitrate
and 100 mg/1 inhibits nitrification by 70 percent. They also noted that, as
nitrification was inhibited, there was a slight rise in the concentration of
nitrite present. This indicates that Nitrobacter is the more sensitive
organism.
The potential toxicity of heavy metals to anaerobic digestion has long
been recognized. Wischmerger and Chapman (1947) noted that sludge digestion,
as measured by gas production, was not retarded at total nickel concentration
up to 500 mg/1. Rudgal (1946) reported a great improvement in digester
performance in a Wisconsin town when a sewage trunkline containing a high
copper load was bypassed into Lake Michigan. Originally there was 3,000 mg/1
of copper in the digester, and it was producing only 0.5 ft3 of gas per pound
of volatile suspended solids added. After bypassing, the gas production rose
to 10 ft3/#V3S added. Stander (1956) showed that toxicity of copper was first
noted between 4,100 and 13,300 mg/kg on a dry solids basis. For that study,
this was about 80 to 270 mg/1. O'Neill (1957) noted that a 1 percent copper
level on a dry solids basis inhibited digester gas production.. He also
concluded that zinc a'ppears to exert a greater effect than copper.
A series of articles (Moore 1961; McDermott 1963, 1962, 1965)
investigated the level of metal in the influent sewage which is inhibitory to
anaerobic digestion. Table 1.4 presents these data. It was also shown that an
anaerobic system does not show a plateau region in response to metal toxicity,
but either proceeds normally or fails entirely and that even though the total
metal concentration is high, the soluble metal concentration is low.
TABLE 14. HIGHEST- CONTINUOUS DOSE OF METAL THAT" WILL ALLOW
SATISFACTORY ANAEROBIC DIGESTION OF SLUDGES (NEUFSLD AM)
HERMANN 1975; MOORE 1961; MCDERMOTT 1963, 1962)
Concentration in Influent
Sewage mg/1
Digested Sludge Metal
Concentration mg/1
Metal
Primary Sludge
Digestion
Combined Sludge
Digestion
Soluble
Total
Chromium
Copper
' Nickel
Zinc
>50
10
>40
10
>50
5
>10
10
3
0.7
1.6
0.1
420
196
70
341
24
-------
Lawrence and McCarty (1965) showed that the soluble metals were
responsible for digester inhibiton and that these could be effectively
controlled by the presence of suifide. Digesters which operated normally at
high total metal concentrations fed as a sulfate failed rapidly when the metal
was fed as a chloride. However, suifide is toxic at high levels (Lawrence et
al. 1964) and can sometimes inhibit a digester. Grady and Lim (1977) present
data showing the soluble metal concentration which is inhibitory to anaerobic
digestion. These data are shown in Table 15. However, Taylor (1965) shows
that soluble zinc causes failure when present in excess of 1.5 rag/1. Gould
and Genetelli (1975) investigated the distribution of seven heavy metals
according to size in an anaerobic digester. More than 90 percent were
associated with the- particulate matter (>100 micron), and for all metals,
except copper, zinc, and lead, the percent in the dissolved state «20
'angstroms) was below the detection limit. Only 0.1 percent of the total
copper, 0.06 percent of zinc, and 0.3 percent lead were dissolved.
TABLE 15. CONCENTRATIONS OF SOLUBLE HEAVY METALS EXHIBITING
50 PERCENT INHIBITION OF ANAEROBIC DIGESTERS
(GRADY AND LIM 1977) _
Approximate Concentration
Metal, mg/1
1-10
_ji
10
Cu* 10
Or*-1- 10
In summary, most authors indicate it is the soluble form of metal which
exhibits toxicity, and the degree of toxicity is dependent upon many
interrelated factors. The major factors are the concentration of organic
matter, both dissolved and suspended, the species of organisms present, and
the chemical environment.
Effects of_ Wastewater Sludges Containing Heavy Metals
The concentration of heavy metals in waste water sludges can be very high,
as shown in Table 10. The direct effect of these metals on treatment
operations, such as anaerobic digestion, was discussed and one would expect to
see inhibition of other biological processes as well. Chemical processing of
sludge, while not subject to inhibition as are biological processes, may
adversely affect the distribution of heavy metals in the sludge. Olver, et
25
-------
al. (1975), showed that chlorine oxidation of sludges releases significant
amounts of metals which are ultimately recirculated within the plant and which
then may be detrimental to the treatment process.
While the 'in-plant effects of heavy metals can be problems for a waste
treatment plant, it is the ultimate disposal of the sludges which poses the
greatest problems. Recently, a large body of literature has been published
and much research done concerning disposal of heavy metal laden sludges to
agricultural land. The key concepts which have been put forth are (Brown
1975): the ability of a plant to absorb metal from a compound depends on
factors other than the solubility of the metal compound in water and that
plant uptake of metals from soils depends on the portion of soil metal called
plant-available metal rather than the total metal content of soils.
Another factor which must be considered is the potential for groundwater
contamination by heavy metals. Olthof (1978) summarized others' work in this
regard, and concluded this does not seem a limiting factor when sludge is
applied to cropland. Large quantities of metals will not be leached out due
to low solubility of metals in a soil-water environment. Solubility depends
on properties of the soil, such as pH, humus and clay content, and cation
exchange capacity.
TJie decision to use land application of sludge must be based on local
conditions and may not be the appropriate disposal technique in every
community. Climate, land use, topography, soil type, and geology are factors
which must be considered. Climate determines such things as length of growing
season, number of days when sludge cannot be applied, and sludge storage
requirements. Topography can influence land application because of runoff and
erosion problems, while geology can determine the potential for"groundwater
pollution. Land use includes such factors as agricultural versus forested
land, reclamation or recreational use. This discussion is limited to
agricultural lands. Soil can be classified by many parameters; the most
important with regard to heavy metals is cation exchange capacity. This is
largely a function of the amount and type of clay present in the soil.
Crop type also influences the amount of sludge which can be applied.
Basically, sludge application rates are usually limited, either by the
quantity of nitrogen in order not to excessively increase nitrate
concentration of groundwater, or by the quantity of potentially toxic
materials, usually heavy metals, specifically cadmium. The lifetime of a
disposal site is usually based on the cumulative amounts of lead, copper,
nickel, zinc, and cadmium applied to the soil. Limits are set forth to allow
growth and use of crops at any future date. Zinc, copper, and nickel will
induce phytotoxicity before their concentrations adversely affect human or
animal health. Lead is a problem because of direct ingestion of soil
particles by animals and sometimes humans, since essentially no plant uptake
of lead occurs. The cadmium limit is derived from its lifetime uptake and
concentration by crops grown in soils amended with cadmium-containing sludges
and the subsequent dangers associated with cadmium being present in the food
chain. The scheme used to determine the amount of sludge which can be applied
to agricultural land is shown in Figure 1 (EPA 1978). Numerical restrictions
are presented in subsequent sections.
26
-------
N Required
by Crop*
Annual Rate
Tons/Acre
I
Cd
Limitation
Lower of
Two Amounts
Total Amount
Tons Sludge/Acre
Controlling Metal
(Pb» Zn, Cu, Ni, Cd)
Figure 1. Approach used to determine sludge application rate and the life
of disposal site.
* Based on many factors such as crop type, previous sludge application,
surface or incorporated application, and available nitrogen.
27
-------
affects o_f Wastewater Treatment Plant Effluent Containing Heavy Metals
The significance of heavy metals in treatment plant effluents, like
wastewater sludges, is a complex subject. There are many parameters other
than metal concentration which determine toxicity to aquatic life and reuse.
Some of these are hardness, pH, and salinity. There are many investigations
studying the problem, as is seen in Table 16 (SPA 1976). Roper (1977) and the
Environmental Protection Agency (1976) indicate that McKee and Wolf, Water
Qualitty Criteria (1963), is an excellent reference summarizing the toxicity
of many contaminants, including metals, to aquatic organisms. Clearly, heavy
metals can exhibit toxicity on aquatic life, can enter food chains via the
water route, and impair subsequent beneficial use of the water.
Regulations
Regulations and proposed standards have been put forth to control the
presence of heavy metals in the system. These regulations have originated on
federal, state, and local government levels. They have addressed three areas:
sludge disposal, effluent requirements, and metal input to the system. The
regulations are in an almost constant state of development and refinement, and
a detailed discussion would be quickly outdated. Nonetheless, some
description is necesaary if only for the purpose of showing the applicability
of the type- of data generated by this investigation.
The Indiana Water Quality Standards indicate that, "All wastes at all
times and all places shall be free from all substances . . . which are in
amounts sufficient to injure, be toxic to, or produce adverse physiological
responses in humans, animals, aquatic _life or plants." It is this section
which can regulate effluent quality. The standards recommend the use of the
96 hr - LCjQ for "biota significant to, the indigenous aquatic conuaunity," and
for fish, to use not more than one-tenth of the 96. hr LC,-a for "important
indigenous aquatic species." The data are to be extracted from Quality
Criteria for Water (EPA 1976) and are presented in Table 17- However, the
current National Pollution Discharge Elimination System (NPDES) permit for
Kokomo does not specifically limit the discharge of heavy metals.
Proposed regulations concerning sludge disposal on agricultural land have
been put forth by the EPA (1977).- They state that the cumulative metal
loading to agricultural land depends on the type of soil present as well as
type of metal considered. Soil type is characterized by the cation exchange
capacity. These loadings are presented in Table 18. There is also a maximum
application rate which shall not be exceeded. This is based on cadmium
loadings and ranges from 0.9 to 1.3 Ib/acre/yr. Indiana has set this value at
1.785 lb/acre/year (2 kg/ha/yr).
The last and most pertinent regulations concerning heavy metal pollution
are those dealing with pretreatment. On June 26, 1978, the EPA (1978) set
final pretreatment regulations to become effective on August 25 of that same
year. This detailed set of regulations was aimed at eliminating the problem
at its source. The regulations apply to nondomestic pollutants discharged
into publicly owned treatment works (POTW's). The standards will be set
nationally on an industry-by-industry basis, using technology-based standards,
but will be enforced in most cases at the state level. The states through the
28
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TABLE 16. EFFECTS OF HEAVY METALS ON AQUATIC BIOTA
Metal Cone .
Cd 57 Ug/1
'
80 ug/1
17 ug/1
8. 1- ug/1
3.4 yg/1
2.0 Ug/1
Cr71 17.6 mg/r
118 mg/1
7.46 mg/1
0.2 mg/1
Cu 60 jig/1
180 ug/1
710 ug/l
Fe- 0..9 mg/1
1-2 mg/1
Effect
Decreased . survival of developing fathead
embryos
minnow
Survival and growth of bluegill sunfish larvae
severely reduced
Growth and survival of channel catfish fry
significantly
Significant reduction in number of eggs
per female of topminnow
Extensive mortality of brook trout during
96-hour LC5Q for Chinook salmon
96-hour LC^a for fathead minnows
96-hour LC50 for bluegill
96-hour LC5Q fOr bluegill (Cr111)
reduced
produced
spawning
Chinook salmon juveniles significantly reduced
Toxic to rainbow trout
96-hour TL5Q brown bullhead
96-hour TL5Q for bluegill
Toxic to carp
Toxic to pike and trout
i
Pb 5-6-7.3 mg/1 96-hour TL50 for fathead minnow
1 mg/1 96-hour TL5Q for rainbow trout
0.10 mg/1 Detrimental effects to brook trout
Ni 730 yg/1 Caused significant reduction in fertility of
fathead minnow
Zn 870 mg/1 96-hour LC5Q for fathead minnows
5.50 mg/1 96-hour LC50 for brook trout
10.6 mg/1 96-hour TL5Q for bluegill
7.8 mg/1 96-hour TL50 for carp
29
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TABLE 17. WATER QUALITY CRITERIA FOR HEAVY METALS (BROWN 1975)
Cadmium .... cladocerans and salmonid fishes
soft water* .... 0.4 yg/1
hard water* .... 1.2 yg/1
for other, less sensitive, aquatic life
soft water* 4.0 yg/1
hard water* .... 12.0 yg/1
Chromium .,
Copper
for freshwater aquatic life ..
for freshwater aquatic life ..
Iron .... for freshwater aquatic life ..
Lead .... for freshwater aquatic life ..
Nickel ..... for freshwater aquatic life ...
Zinc .... for freshwater aquatic life
100 g/1
0.1 times a 96-hour LC5Q as
determined through nonaerated
bioassay using a sensitive
aquatic resident species
.. 1.0 mg/1
.. 0.01 times the 9"6-hour LCeQ
using the receiving or
comparable water as the
diluent and soluble lead
measurements using a 0.45
micron filter
0.01 times the 96-hour LC5Q
of sensitive resident species
0.01 times the 96-hour LC5Q
of sensitive resident species
30
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TABLE 18. MAXIMUM SLUDGE METAL APPLICATIONS
FOR PRIVATELY OWNED FARMLAND
Soil Cation Exchange Capacity (meq/100 g)
<5 5-14.9 y\5
Maximum Metal Addition Ib/acre
Lead
Zine
Copper
Nickel
Cadmium
450
225
113
45
4.5
900
450
225
90
9
1800
900
450
180
18
Note-: 1.785 Ib/acre = 2 kg/hectare.
NPDES system will have the power to modify the standards to suit local
conditions. Specifically a POTW has to implement a pretreatment program which
reflects the removal capability by the POTW.
This regulation applies to all POTW's with a flow of at least 5 mgd and
receiving any industrial wastes, and those less than 5 mgd if tn~e situation
warrants it. The POTW must (1) require compliance with federal standards, (2)
control, through contract, permit, or other means, the discharge of the
industrial user, (3) develop a compliance schedule for installation of
technology to meet applicable pretreatment standards, and (4) inspect and
monitor discharges. In addition, the POTW must (1) identify and locate all
industrial users subject to the regulations, (2) identify the character and
volume of the above flow, (3) set up a notification-monitoring system for
those industries affected, (4) pursue legal action against noncorapliers, and
(5) provide sufficient funding, personnel, and expertise to carry out these
objectives.
As stated above, the POTW can relax a pretreatment regulation on the
basis of its removal efficiency for that pollutant according to the formula:
where Y = modified standard
X = national standard
r = POTW removal efficiency
31
-------
However, when a POTW revises a categorical pretreatment standard, a
partnership is formed in which both the POTW and discharger assume
responsibility for meeting the pretreatment standard. It is further stated
that a POTW may revise these regulations only if (1) the pollutant is
consistently 'removed (documented removal occurs in 95 percent of
representative samples taken) and the POTW cannot be by-passing any sewage or
has completed an analysis to implement a by-pass control project, or (2) the
sludge disposal practice is currently and will continue to meet the
appropriate regulations.
On May 22, 1978, the City of Kokomo passed ordinance 4644 (amended
ordinance 4126) which set the following concentration limits for industrial
dischargers of heavy metals: Cd (0.5 mg/1), Cr (2.5 mg/1), Cr -6 (2.5 mg/1),
Cu (2.0 mg/1), Mi (2.0 mg/1), Zn (5.0 mg/1), lead (0.5 mg/1), and iron (5.0
mg/1).
32
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SECTION THREE
FIELD INVESTIGATION OF HEAVY METAL MASS FLOW IN AND AROUND
THE KOKOMO, INDIANA, SEWAGE TREATMENT PLANT
INTRODUCTION
This investigation determines in some detail the mass flow pattern of
heavy metals within a full-scale municipal treatment plant receiving a fairly
high level of influent heavy metals. Specifically, a mass balance was
performed around each unit operation, and around the plant as a whole. A
second objective was to demonstrate that a program of this type is feasible at
a treatment plant and that data are generated that can ultimately be used in
formulation of a municipal sewer use ordinance to regulate point sources of
heavy metals. Finall'y. the data generated by this study enable examination of
the effect of various sludge systems and influent heavy metals on plant
operation. For example, it allows comparison of heavy metal levels with
changes in sludge-handling procedures.
The treatment plant selected for this study was a 30 mgd activated
sludge, multimedia gravity filter plant at Kokomo,- Indiana, which is located
about 50 miles directly east of Purdue University in West Lafayette, Indiana.
The plant location, layout, and flow diagrams are shown in Figures 2, 3» and
4, respectively. This particular plant was chosen for several reasons: the
size of the community (42,000), the industrial makeup, and its proximity to
West Lafayette. A medium-sized city was chosen in order to guarantee that the
sewage would be of "typical" composition, i.e., that niether an overabundance
of domestic nor industrial sources discharge to the sewage system. More
important, Kokomo was chosen because of its industrial makeup, which includes
such metal dischargers as plating shops (Cd, Cr, Cu, Ni, Zn), alloy
fabricators, electronics equipment manufacturers, a steel mill, various cold-
working metal shops, and printing presses. These industries contribute
substantial quantities of heavy metals which have been a problem to the
treatment plant for some time.
Cadmium, chromium, copper, nickel, and zinc are the five heavy metals
chosen for this study because of their potential effects on the environment,
particularly in land disposal of sludge and subsequent phytotoxicity of cover
crops. The similarity and ease of analysis of these metals using atomic
absorption spectrophotometry was also a factor because of the large number of
samples expected and the necessity for rapid analysis. This was the reason
for excluding mercury, a problem metal. The final reason for selecting these
metals was their presence in Kokomo's sewage and sludge at atypically high
levels.
33
-------
0 fmi. 2 mi.
CO.RD.300N.
KOKOMO
0 I
PURDUE
INDIANAPOLIS
KOKOMO STP
o
o
04
d
-------
CO
(U
«-*
cu
*<
o
c
rt
Backwash
CO
en
O-1
Skimmings
Tank
Supernatant
11
,(^
is
10:
i
£
Holding
Tank
Zimpro Vacuum
Zimpro Thickener Filters
, r\ __
1 \J 7...
Zimpro Supernatant
Filtrate
Filter Cake
Main Stream Operation
Sludge Stream; Including Activated Sludge
Recirculation Streams
-------
Chem. Add. - Chemical Addition for Phosphoruus Removal; not operational.
dp Contact - Chlorine Contact Tank*
Grit ' - Grit Chamber.
Pri - 1
- 2 - Primary Settlers; Numbers as per Kokomo Treatment Plant
- 3 Convention.
- 4
Sec. Clar. - Secondary Clarifiers.
Skim. - Skimmings Holding Tank.
31. Hold. Tank - Raw Sludge Holding Tanks.
V. F. Build. - Vacuuum Filter Building.
Zimpro Service - Zimpro Service Building.
Zinu Thi. - Zimpro Thickener»
Filters - Multi-media Gravity Filters
Aerators Activated Sludge Aeration Basins.
TL 1-6 - Trunk Line- #1-6.
Figure 3,. continued.
36
-------
Parshali
Flume
Filters
nfluent M.H.
Figure 4. Process flow diagram.
37
-------
During the study, intermediate results were generated to allow evaluation
and perhaps modification of the sampling program. One intermediate evaluation
showed an unusually high level of metal removal across the entire plant
relative to value reported at similar facilities elsewhere. This led to
inclusion of iron as a metal to be measured because of its possible effects on
removal efficiencies. Lead was added to the project at the same time because
of other research on the sources of heavy metals to the Kokomo sewer.
The sampling period necessary for the mass balance must be at least as
great as the retention time of any of the tanks of solids or liquid-handling
system enumerated in Table 19 and also greater than the mean cell residence
time of activated sludge. A further consideration was a sampling period of
sufficient duration to minimize the effect of a widely varying metal load to
the plant because of weekdays and holidays. A 60-day period was decided upon,
commencing at 12 noon, August 2, 1978, and continuing through 12 noon, October
1, 1978. The mass balance for iron and lead was undertaken from September 6,
1978, through September 16, 1978, inclusive, an 11-day period encompassing
days 35 through 45 of the sampling program.
TASLS 19. RETENTION TIMES OF THE VARIOUS PROCESS TANKS AT KOKOMO, INDIANA
Process Tank Volume (MG) Retention Time (Hours)
Grit Chamber
Primaries
Aerators
Secondaries
C12 Contact Chamber
Gravity Filters
Haw Sludge Holding Tank
Zimpro Thickener
0.18
1.2
5.4
4.7
0.46
0.67
0-2.2
0.33
0.3
1.3
3.2
3-1
0.6
0.9
0-280
103
1 Based on actual hydraulic flow rate through system as reported in
Table 27, and pro-rated for a 60 day period for intermittent systems.
LABORATORY APPARATUS AND PROCEDURES
The large number of samples necessitated instituting a system for orderly
analysis.
38
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Sample Preservation
Samples were brought from Kokomo on a routine basis. At Purdue they were
acidified to a. pH of 2 with 1:1 HNO,. It was found that this could be
accomplished through the addition of 1 ml of 50 percent nitric acid per 125 ml
of sample. At the beginning of the 60-day period, the nitric acid was added
directly to the empty bottles before sampling. This led to numerous and
justifiable complaints from the plant personnel about acid burns and fumes.
Therefore, from day 5 of sampling, acid was not added until the samples were
returned to Purdue. Since it is recommended (Taras 1975; SPA 197*0 that the
acid be added immediately upon collection of the sample, the effect of not
adding acid until late was investigated. This consisted of removing a series
of aliquots from a large volume of sample. Acid was added to each of these
according to the schedule in Table 20. These samples were subsequently
handled in the same way as the actual mass balance samples. The results of
this determination are shown in Figure 5 and indicate that no appreciable
error is introduced by delaying acid addition as much as three days.
TABLE 20. ACID ADDITION SCHEDULE USED TO INVESTIGATE THE EFFECTS
OF DELAYED ACID ADDITION FOR SAMPLE PRESERVATION
Sample Mo. When Acid Added
1 Immediately on collection
2 12 hrs. after collection
3 26 hrs. after collection
4 . 72 hrs. after collection
5 121 hrs. after collection
6 20 hrs. prior to analysis
(148 hrs. after collection)
7 Immediately prior to analysis
(168 hrs. after collection)
8 None added
Analytical Methods
The liquid samples were composited in proportion to flow rate and
analyzed. The metals which were determined (cadmium, chromium, copper,
nickel, zinc, and later iron and lead) were analyzed according to the
procedure outlined in Manual c_f Methods for Chemical Analyses c_f Water and
Wastes (EPA 1974), with only minor modifications, as noted in Appendix A. The
method entails slowly evaporating an aliquot of the sample to which 5.0 ml of
concentrated HNO^ has been added, of the sample to dryness. After the beaker
39
-------
2.5
O)
E
c
o
o
o
c
o
o
o
-t
o>
2.0-
1.5 -
1.0-
0.5
Zn (no acid*21.9 mg./l)
(no acid =2.16 mg./l)
Cu (no acid= 1.76 mg./l)
Note- Zn concentration
reduced by factor of
ten for graphing purposes.
Cd (no acid = 0.412 mg./l)
I 23456
Days After Collection that Acid was Added
Figure 5. Effect of acid addition on metal concentration.
-------
and sample cool, another 5 ml portion of nitric acid is added, the beaker is
covered with a watch glass and refluxed for 90 minutes. Hydrochloric acid is
added, and the mixture is then refluxed for another 90 minutes. The watch
glass is then removed and the acid mixture allowed to evaporate to dryness.
After cooling 10 ml of 1:1 HNO,, made with double distilled de-ionized water,
is added and allowed to remain in the beaker until all residue dissolves,
generally for about 5 minutes. This is the sample which is analyzed and is
transferred to a plastic 50 ml dilution tube. Through experience, it was
found that a 1:10 dilution and 1:100 dilution was necessary so that the Atomic
Absorption spectrophotometers can-operate within the linear range of the
absorption-metal concentration curve.' These dilutions were also prepared with
a 10 ml glass repipet and 1.00 ml Eppendorf pipette*.
Vacuum filter cake samples were collected and placed in small plastic
bags by plant personnel. On reaching Purdue samples were immediately placed
in the freezer until analysis; no acid was added. They were then analyzed,
using the modified method discussed previously and in Appendix A, after being
heated to dryness so the total solids content could be determined.
Equipment
All samples were collected in wide-mouth plastic bottles of three sizes,
159 ml, 250 ml, and 500 ml, with screw-on caps. The composited samples were
subsequently placed in 200 ml Berzelius beakers for digestion. Either
volumetric glassware or a Mettler P-1210, 1200 g capacity balance was used to
measure the amount of sample subject to digestion. All evaporations and
digestions were done on four identical Corning PC-100 Hot Plates located under
a standard laboratory hood. The metals were determined on two .Perkin-Elmer
A.A.S. The older instrument, a PS 306, was used for approximately the first
20 days of the sampling- period. The second machine, a PE 603, was used for
the remainder of the project. Both machines utilized a Deuterium Arc
Background Corrector to correct for the high concentration of salts which
developed, when samples are evaporated. The settings and operational
conditions of the instruments are discussed in Appendix B.
Standards were prepared from commercial stock solutions obtained from
Harleco Chemicals. A working stock solution was prepared from the commercial
stock solution. This, in turn, was used to prepare the sequential dilutions
used in actual determinations. Table 21 shows concentrations of various
metals in sequential dilutions used in the standards; these were identified as
2A, A, B, C, D, E. A sequence of six 1:1 dilutions was used. The standards
were prepared as needed, with the exception of chromium, which was prepared
fresh weekly.
Accuracy and Precision
The accuracy and precision of the atomic absorption technique have been
determined many times- and are readily available (Taras 1975; SPA 1974). Those
data, however, can only be applied to the particular technique used and the
individual laboratory or laboratories where the analyses were performed. To
use the modified technique, it was desirable to obtain accuracy and precision
data which includes all the variables of this analytical method, including the
41
-------
instruments, technique, and analyst. Furthermore, accuracy and precision are
functions of the concentration of the metal being analyzed, and therefore
determinations should be done for varying metal levels.
TABLE 21. METAL CONCENTRATION IN SEQUENTIAL DILUTIONS USED TO
STANDARDIZE INSTRUMENT
Metal Concentration (mg/1)
Standard
Metal 2A A B C D E
Cd
Cr
Cu
Mi
Zn
Fe
Pb
2.00
10.00
10.00
2.00
100.00
40.00
1.00
2.00
5.00
5.00
1.00
50.00
20.00
0.500
1.00
2.50
2.50
0.500
25.00
10.00
0.250
0.500
1.25 '
1.25
0.250
12.50
5.00
0.125
0.250
0.625
0.625
0.125
6.25
2.50
0.0625
0. 125
0.3125
0.3125
0.0625
3.125
1.25
The accuracy of each metal analysis was to be determined at^four levels:
highr intermediate-high,- intermediate-low, and low. Divisions were made on
the basis of the working standard, concentration "A", given in Table 21. The
divisions occur at: greater than 80 percent, "A" standard; 50 to 80 percent,
"A" standard; 20 to 50 percent, "A" standard; and less than 20 percent, "A"
standard, respectively. The results of 15 replicate samples in each range for
each metal are shown in Table 22 and Figure 6. It can be seen that the
precision of the method is greatest at a higher metal concentration, but not
so high that the nonlinear range is used. It is emphasized that these results
are in terms of the concentration of metal in the solution being analyzed, not
in the original samples since it is the concentration in the solution
aspirated by the instrument which will affect the instrument and hence the
precision of the method. This is the basis for determining how far to
concentrate a sample.
The accuracy of the method can be estimated by addition of a known volume
of a solution of a known metal concentration and then determination of the
amount of metal present above the background level and comparison to the mass
of metal added. When this is done, the results are expressed as "percent
recovery." Ideally it should be 100 percent. The results are shown in Table
23. derived from tests run on 10 samples. It can be seen that the method is
reasonably accurate.
-------
TABLE 22. PRECISION OF METAL ANALYSES
Metal
Cd
Cr
Cu
Ni
2n
Metal
Cd
Cr
Cu
Ni
Zn
High
Abs . Range
(Cone, mg/1)
94-205
O0.8)
119-151
O1.6)
232-431
O4.0)
175-233
O4.0)
2lf-269
O0.3)
Intermediate
Aba. Range
(Cone., mg/1)
40-63
(0.2-0^,5)
9-29
(0.4-1.0)
61-75
(1.0-2.5)
25-62
(1.0-2.5)
21-40
(0.2-0.5)
Relative1
Stan . Dev .
5.9?
4.3?
2.5%
3.6%
3.3?
- Low
Relative1
Stan. Dev.
25.0?
22.7?
3.7$
8.7?
118.5?
Intermediate - High
Abs. Range Relative
(Cone, mg/1) Stan. Dev.
69-84
(0.5-0.8)
61-105
(1.0-1.6)
123-157
X2.5-4.0)
60-92
(2.5-4.0)
32-74
(0.5-0.8)
Abs. Range
(Cone, mg/1)
0.5-3
«0.2)
3-7
«0.4)
1-4
«1.0)
13-20
«1.0)
5-9
«0.2)
4.1?
4.2?
3-7?
4.4?
7.3?
Low
Relative1
Stan. Dev.
63.0?
40.9?
67.5?
20.6?
16.3?
1 Relative standard deviation equals the standard deviation divided by the
average, multiplied by 100.
43
-------
70-
60-
5 50-
CD
<
CL
c
o
40-
30-
a
a
oo
20-
a>
o:
10-
Q Cadmium
O Chromium
G Copper
A Nickel
Q Zinc
Note- See Table22 for
appropriate concentrations
of metals in each range.
Each metal is different
owing to differences in
analytical sensitivity of
technique*
Low Int-Low Ini-High High
Metal Concentrations
Figure 6. Precision of metal analyses.
44
-------
TABLE 23. ACCURACY OF METAL ANALYSES
Metal'% Recovery
Cd
Cr
Cu
Ni
Zn
93.1
93.0
96.2
97.4
96.8
1 Percent of metal in a known synthetic spike which
accounted for during analysis.
(Conc.;in spiked sample) x (Vol. of spiked sample) - -
(Cone, in sample) x (Vol. of sample)
% Recovery = (Cone, of spike) x (Vol. of spike) x 100S
SAMPLING PROGHAM
To obtain a useful heavy metal mass balance around a municipal treatment
plant such as Kokomo's, each sampling point must be carefully chosen. The
exact location for a sampling point must meet the following requirements:
(1) It must be easily accessible to treatment plant personnel;
(2) The flow rate at the sampling point must be determinable, and
(3) It must be located so that a representative sample can be
easily collected.
Conceptual Location of Sampling Points
Before exact locations are specified, however, a decision must be made of
what flow streams need to be sampled. The starting point for this is Figure
4, the plant flow diagram. This shows that there are several interconnecting
recirculation loops, e.g., the filter backwash and waste sludge streams. An
expanded version of Figure 4 is shown in Figure 7, which clearly labels the
needed influent and effluent streams for a mass balance from every unit
operation, as well as three "mixing points."
Mixing points can be thought of. as a unit operation which serves the same
purpose as completely mixed reactors. The use of mixing points accounts for
metals in the interlocking loops. For example, mixing point 2 connects the
grit chamber effluent and the primary influent, the connection being the
pounds of metal present in the waste-activated sludge and filter backwash.
45
-------
RAS
i
yv
a:
uj
H
GRIT
^\ GR CH,
J INE
GRIT
CHAM.
GR.CHJ'M
EFE VJ
P\ PR! ,
l) INF.
SET.
*i
<»:
RAW.
SLUD.
HOLD
a.-
in
Pfti Yw
EFF X
Zl
r~
i
"ziMFEEd
\
IP\ AER
L/ INF.
AERATOR
AER.
EFF *
M^BYjPASS
ZIM.
SYS.
O2SLUD
ZIM.
THICK.
m
M
SEC. SEC GRAV. PL
SET. EFF.' FILT. EFF
LAGOON FEED
VF.FEEP* ^C CAKE ,
' FIL. *
C
i
Figure 7. Mass balance diagram.
-------
PL. INF.
GR. CH. INF.
GR. CH. SFF.
PHI. INF.'
PRI. EFF.
AER. INF.
ASH. EFF.
SEC. EFF.
PL. EFF.
GRIT
WAS-R.
WAS-U.
FILTER B.W.
RAW SL.
ZIM. FEED
CU SLUD.
VTF. FEED
CAKE
SUP.
ZIM. SUP.
ZIM.. BY-PASS
LAGOON FEED
MP 1
GRIT CHAM.
MP 2
PRIM. SET.
MP 3
AERATOR
SEC. SET,
GRAY. FILT.
RAW SLUD. HOLD.
ZIM. SYS.
ZIM. THICK.
VAC. FIL.
- Plant Influent
- Grit Chamber Influent
- Griit Chamber Effluent
- Primary Influent
- Primary Effluent
- Aerator Influent
- Aerator Effluent
- Secondary Settler Effluent
- Plant Effluent
- Grit
- Waste Activated Sludge from Aerators
- Waste Activated Sludge from Underflow
- Filter Backwash
- Raw- Sludge
- Zimpro Feed Sludge
- Oxidized Sludge
- Vacuum Filter Feed
- Filter Cake
- Raw Sludge Holding Tank Supernatant
- Zimpro Thickener Supernatant _.
- Filtrate
- Zimpro By-Pass
Lagoon Feed
- Mixing Point 1
- Grit Chamber
- Mixing Point 2
- Primary Settlers
- Mixing Point 3
- Aerators
- Secondary Settlers
- Gravity Filters
- Raw Sludge Holding Tank
- Zimpro System Reactors
- Zimpro System Thickener
- Vacuum Filters
Figure 7, continued.
-------
Theoreticaly, a mixing point could be placed at the intersection of any of the
recycle streams, such as the Zimpro supernatant and vacuum filter filtrate.
Four streams are not shown in the flow diagram of the plant. Two of
these are the'primary and secondary skimmings streams. The secondary
skimmings flow to the same recirculation loop as do waste-activated sludge and
filter backwash. The primary skimmings are sent to a 81,000 gal holding tank.
The skimmings were excluded from the sampling program because of the very
small volume relative to the other streams. The consequent long retention
time of the holding tank (it is emptied by a contractor about once per year)
tends to make this stream's metal load insignificant. However, this is not
that there is not a'high metal level in the skimmings, as later data show,
thus disposal of skimmings should be carefully evaluated. Another stream not
shown flows from the chlorine contact chamber eventually to mixing point 1.
Periodically, plant personnel open a valve which allows any sludge accumulated
at the bottom of the chlorine contact tank to be recirculated to the system.
It was felt that the intermittent nature of this stream, as well as its
relatively low flow rate, would be insignificant in any mass balance performed
about the chlorine contact tank. A fourth stream not shown is the screenings
from the bar rack. Screenings consist almost entirely of rags and debris
which constitute a very small portion of the influent waste flow and are
inconsequential in terms of the heavy metals mass balance.
Two other streams, indicated by dashed lines in Figure 7, are necessary
because plant operation problems forced modifications in the system causing
layoff for short periods. The Zimpro bypass stream arose early in the project
when the Zimpro system was out of service and it became necessary to lime the
raw sludge so it could be vacuum-filtered and disposed. The lagoqn-fed stream
arose when mechanical problems were experienced with the vacuum filters, and
as a result, the Zimpro thickener was overloaded. Thus it became necessary to
pump sludge from the thickener to the old sludge lagoon at the rear of the
treatment plant-
Two other terms will eventually be necessary to complete the mass
balance. These1 are accumulation terms for the Zimpro thickener, which was
initially empty, and for the raw sludge holding tank, which has a floating
cover and, therefore, has a variable inventory.
Physical Location of Sampling Points
Figure 7, the detailed flow diagram, Figure 3, the plant layout and the
criteria listed at the beginning of this section describe each sampling point.
The method of flow measurement is covered in a subsequent section.
There are two distinct systems within the treatment plant. One is the
mainstream system which functions to reduce the concentration of pollutants in
wastewater. The other system handles sludge, and its function is to increase
the solids concentration and hence metal level. The consequence of this
distinction is that the flow rate in the first stream is essentially conserved
from influent to effluent, while in the sludge stream it is radically reduced.
-------
The first sampling point is the plant influent. The fist choice was to
sample at the wet well of the pump station, however, the wet well is mixing
point 1 (MP1), Therefore, it was necessary to find an upstream sampling
point, a manhole on the plant site through which pass five of the six trunk
lines that serve Kokomo. The sixth trunk line serves only domestic sources
and does not contribute significant metal or hydraulic loads to the plant, as
shown in Table 24. It was decided that this manhole would serve as the
sampling site. It is also the site at which the plant has routinely sampled
its influent in the past.
TABLE 24. HYDRAULIC AND METAL LOADING TO TREATMENNT PLANT FROM LONE
TRUNKLINE NOT SNTERINNG THROUGH PLANT INFLUENT MANHOLE
Flow
Day MGD Cd
1 0.380 0.002
2 0.478 0.001
3 0-406 0.001
Avg. 0. 42T 0.001
Metal Load
Cr Cu
0.02
0.008
0,014
0.014
0.15
0.118
0.141
0*136
(#/day)
MI
0.02
0.014
0.025
0.020
Zn
0.30
0.122
0.166
0.196
Pb
0.05
0.016
0.027
0.031
Percent of
Total Plant 2.4% 0.02?. 0.01 J 0.56? 0.02? 0.07? 0.44?
The influent and' effluent to the grit chamber were sampled at respective
ends of the chamber. Care was needed in sampling the effluent because of the
design of the grit chamber in Kokomo. The sample must be taken upstream of
the overflow at the grit chamber effluent, because the downstream side of the
overflow is essentially mixing point 2, where the waste sludge and filter
backwash streams re-enter the mainstream.
Samples of grit were periodically collected on a grab basis. The grit
was raked to the influent end of the aerated grit chamber and then
mechanically lifted to a screw conveyor which transported it to a small truck
next to the building. Due to moving equipment, it was unsafe to sample from
the screw conveyor, and due to the nonhomogenous state of the grit, once in
the truck, sampling was done as it dropped from the screw conveyor onto the
truck. Because of the small mass flow rate, only a rough estimate of metal in
the grit was necessary.
Influent to the primaries was perhaps the most difficult point to sample.
There was no place open to sample between mixing point 2 and the primaries and
no splitting box between mixing point 2 and the four primaries.
Consequently, it was necessary to sample at each primary and composite the
samples. A scheme was devised to composite samples as they were collected to
minimize the number of bottles. Since samples should be composited by flow
49
-------
rate, it was necessary to assume that the overflow rate for each primary was
equal. This implies that the samples could be composited according to surface
area of the settlers. Only 500 ml bottles were used, and they were marked
with appropriate lines and in a designated order, shown in Figure 8.
The primary effluent was sampled at the collection box located near the
aeration building. It was necessary for plant personnel to ascertain that no
floating material was collected in the sample.
The aeration influent, aeration effluent, and waste activated sludge
were, in effect, samples of the mixed liquor. Only one sample was collected
due to the homogeno'us nature of the mixed liquor with respect to the heavy
metals. At Purdue, this sample was composited according to both the aeration
influent flow rate and the WAS flow rate. The two different composites
reflected the difference in flow rate of the two streams. Each composite was
analyzed individually.
The return activated sludge was sampled at a pre-existing sampling port
in the aeration building basement. When sampling at this point, first it was
necessary to open a faucet and let it run for about 30 seconds to empty the 20
ft vertical section of sampling pipe leading from the HAS line to the sampling
point.
At times, sludge was wasted from the underflow of the secondary
clarifiers (WAS-U stream). When this occurred, a portion of the HAS samples
was composited according to the flow rate of the WAS-U stream and analyzed
separately.
The secondary effluent was sampled at the Parshall Flume where there was
a good deal of turbulence, assuring a representative sample. The flow rate
was also measured here to assure accuracy.
The plant effluent was sampled at the clear well of the gravity filters.
From there it flows through an outfall to Wildcat Creek. The clear well was
chosen rather than the outfall simply because the Kokorao plant routinely
samples at that point.
The filter backwash was sampled at the surge tank adjacent to the filter
gallaries because of its convenient location. It also gives a more
representative sample than would the filter itself due to the changing
characteristics of the backwash water.
The preceding sampling points constitute the sampling program for the
main stream operations. Sight other sampling points constitute the sludge-
processing system. The two systems are interfaced through the raw sludge
stream and mixing point 1.
The raw sludge was sampled at a pre-existing sampling port adjacent to
the piston pumps which pump the sludge from the primary clarifiers to the raw
sludge holding tank. These are located in the basement of the vacuum filter
building. One sample was taken each time sludge was pumped from a different
50
-------
Figure. 8. Bottle used to sample primary influent.
5]
-------
primary. Sampling was done near the midpoint of the pumping period to avoid
getting an excessively dilute or concentrated sludge sample.
Periodically the plant would supernate a volume of liquid from the raw
sludge holding' tanks to the wet well. Then a sample was collected at a
sampling port installed in the basement of the vacuum filter building in the
pipe leading to the wet well. Samples were collected at approximately the
midpoint of the supernating operation.
The Zimpro feed and oxidized sludge streams, the influent and effluent
from the Zimpro reactors, respectively, were sampled at pre-existing sampling
ports in the Zimpro 'service building by the operators. Needless to say, these
samples were only collected when the Zimpro system was on-line.
The Zimpro supernatant sample was collected by the operators at a sump
adjacent to the Zimpro thickener. This supernatant was collected as it flowed
over a triangular weir constructed in the sump for flow measurement purposes.
There were periods when this stream was not flowing, even when the Zimpro was
operating, due to the liquid level in the thickener being drawn down by
feeding the vacuum filters. Samples were collected only when there was a
flow.
The vacuum filter feed was sampled directly from the vacuum filter
troughs. This gave the most representative sample for this stream because of
the mixing of the sludge in the trough caused by rotation of the filter.
Again, this sample was collected only when the filters were operational.
The sample of the filtrate- from the vacuum filter was collected from the
same point as was the supernatant from the raw sludge holding tank for two
reasons. First, the filtrate and the supernatant flow through the same pipe
to the wet well, and second, the piping system is arranged so that only one of
the operations can be done at a time. Thus there is no mixing of the two-
streams .
The last major stream is the filter cake. At Kokomo, the cake is removed
from the vacuum filters and then transported to trucks by a conveyor belt.
The vacuum filter operators removed typical pieces from the conveyor and place
them in plastic bags, which were sealed and transported to Purdue for
analysis.
The Zimpro bypass which occurred when the plant limed the sludge, was
sampled in a manner analogous to the vacuum filter feed, i.e., in the trough
of the vacuum filters The lagoon feed was never actually sampled since this
stream was discovered after the project began. The sludge was pumped from the
bottom of the Zimpro thickener to the lagoon, and because of this, the metal
concentration was estimated as the average concentration fed to the vacuum
filters.
The accumulation in the raw sludge holding tank was estimated as the
average concentration of raw sludge fed to it thoughout the 60-day period.
The concentration of accumulation in the Zimpro thickener was assumed to be
identical to that of the vacuum filter feed because initially the thickener
52
-------
was empty and during the last ten days of the project, sludge was continually
added from the Zimpro system while none was removed by vacuum filters, thus
the thickener was nearly filled with thickened sludge. This was verified
chamber influent increased dramatically from the previous 50-day level. The
increased solids lost over the weir of the thickener due to the buildup of
sludge in it caused this.
Flow Measurement
During the 60-day study, the Kokomo plant was still in a facilities
expansion program and not all electrical control systems were operational, so
often there was no direct measure of a stream's flow- rate. This necessitated
a system of addition and subtraction of known flows to determine an unknown
one.
When the project started, the only automatic flow-measuring devices which
were completely operational were the Parshall Frume, the totalizer meter
measuring filter backwash, and the Zimpro flow measurement devices. Other
systems were only partially operational, such as measurement of the waste
sludge stream, or not operational at all, such as meters monitoring flow to
the primaries. Even- though flow meters on the waste-activated sludge and
return activated sludge lines were initially inseparable, a method was devised
to measure flow rates, explained in Appendix C.
Referring to Figure 7, the only streams directly known in the mainstream
system are the secondary effluent and the filter backwash. The waste sludge
and return sludge are known indirectly. The -other streams must be obtained
through hydraulic balances about the various unit operations and groups of
unit operations. ~"
Plant effluent: Hydraulic balance about gravity filters. PL. EFF. =
(SEC. EFF.) - (FILTER B.W.)
Plant influent: Hydraulic balance about main stream system, assuming raw
sludge stream is approximately equal to the recycle to mixing point
2. PL. INF = PL. EFF
Grit chamber influent: Hydraulic balance about mixing point 1. GR. CH.
INF = (PL. INF.) + (RAW SL.)
Grit chamber effluent: Hydraulic balance about grit chamber, assuming
grit volume is negligible. GR. CH. EFF. = GH. CH. INF.
Primary influent: Hydraulic balance about primary settler. PRI INF =
(GR. CH. EFF) + (WAS) -K (FILTER B.W.)
Primary effluent: Hydraulic balance about primary settler. PRI EFF =
(PRI INF) - (RAW SL.)
Aeration influent: Hydraulic balance about mixing point 3. AER INF =
(PRI EFF) H- (RAS)
53
-------
Aeration effluent: Hydraulic balance about aerators. AER. EFF = (AER
INF) - (WAS - H).
The simplified sequential equalities above are expressed in terms of
known quantities only. Table 25 summarizes flow calculations.
In contrast to mainstream operations, most flows in the sludge stream are
directly measured. Raw sludge and vacuum filter-feed flow rates are measured
by stroke counters on respective piston pumps (the volume of one stroke is 2.9
ft3). The Zimpro feed and oxidized sludge flow streams are measured
automatically by the Zimpro system. The volume of supernatant from the raw
sludge holding tank was calcuated, knowing the diameter of tanks and levels of
floating covers before and after supernating (1 in = 3,540 gal). The volume
of filter cake produced was obtained from invoices by Caldwell Gravel Sales,
Inc., a private contractor who hauls away the sludge cake. The weight of
filter cake on the truck is on a wet-weight basis, and thus any attempt to
calculate a mass flow rate of heavy metals must utilize a concentration
expressed on a wet-weight basis. The Zimpro supernatant was initially
measured with a V-notch weir constructed in the overflow sump adjacent to the
Zimpro thickener. About two-thirds of the way through the project, the weir
was removed by treatment plant personnel because it was causing a buildup of
solids in the sump and effluent weir within the thickener. After that time,
flow was estimated by a hydraulic balance on the Zimpro thickener, taking into
account the discontinuous nature of the influent oxidized sludge stream and
effluent vacuum filter-feed stream. The flow rate of the filtrate was
estimated by a water balance around the vacuum filters. The mass of solids in
these sludges was considered, explained more fully in Appendix C.
The Zimpro bypass stream was pumped by the same pumps used for the vacuum
filter-feed stream, so its flow rate was measured by the stroke counter on
those pumps. The lagoon feed stream was also pumped by those pumps, so its
flow rate was measured in an analogous manner. The volume of grit produced
was estimated by multiplying the number of times the grit truck was dumped by
the volume it carried. Plant personnel estimated about 20 ft3/truck, which
agrees with the estimate of a typical conical pile of grit three feet high and
five feet in diameter measured during the study.
The volumes of the two accumulations were also determined. The raw
sludge holding tanks were equipped with floating covers, and the initial and
final depths of sludge were used to calculate the net accumulation. The
volume of accumulation in the Zimpro thickener was the volume of the
thickener, since it was empty at the beginning and completely full at the end
of the 60-day period. Table 26 summarizes this information.
Sampling Logistics
It became necessary to establish a routine to collect, transport, and
analyze the large number of samples. First, the frequency of sampling
necessary to establish a good mass balance was determined. For mainstream
operations, this was determined by a trade-off between accuracy of the mass
balance (better as more samples were collected) versus the time involved in
collecting and analyzing (better as fewer samples were collected). Initially
-------
TABLE 25. FLOW CALCULATION FORMULAS FOR MAIN STREAM SYSTEM
Stream
Flow Formula
PL. INF.
GR. CH. INF.
GH. CH. EFF.
PHI. INF. ;
PHI. EFF.
AER. INF.
AEH, EFF.
SEC.- EFF.
PLANT EFF.
WAS
RAS
FILTEH B.W.
RAW SL.
GRIT
(SEC. EFF.) - (FILTER B.W.)
(SEC. EFF.) - (FILTER B.W.) + (RAW SL.)
(SEC. EFF.) - (FILTER B.W.) * (RAW SL.)
(SEC. EFF.) * (WAS) + (RAW SL.)
(SEC. EFF.) + (WAS)
(SEC. EFF.) +. (WAS) * (RAS)
(SEC. EFF.) + (RAS)
SEC. EFF., Parshall Flume
(SEC. EFF.) - (FILTER B.W.)
WAS, as per Appendix C
RAS, as per appendix C
FILTER B.W., Totalizer
RAW SL., Stroke Counter on Piston Pump
GRIT, i.e., 20 ft3/truckload
55
-------
TABLE 26. FLOW CALCULATION FORMULAS FOR SLUDGE STREAM SYSTEM
Stream
Flow Formula
RAW SLUDGE
ZIM. FEED
02 SLUDGE
V. F. FEED '
CAKE
SUP.
ZIM. SUP.
FILTRATE
ZIM. BY-PASS
LAGOON FEED
2.9 x (STROKES ON PISTON PUMP)
Directly from Zimpro System
Directly from Zimpro System
2.9 x (STROKES ON PISTON PUMP)
From Innvoices of Sludge Hauler
(3540 gal.) x (in. of Supernatant)
Q = 2.5H2-5 for weir (Q in cfs, H in ft.)
(02 SLUDGE) - (V. F. FEED)
As per Appendix C
2.9 x (STROKES ON PISTON PUMP)
2.9 x (STROKES ON PISTON PUMP)
there was a two-hour sampling frequency, but it was unworkable, with not
enough time allowed' to analyze samples and too much time taken by plant
personnel. Thus, after day 5 the sampling interval was increased to four
hours, cutting the time spent sampling in half and allowing twice as long with
analysis. An intermediate calculation of mass balance progress was done on
day 18 and showed no inaccuracy compared to one done after day 6. The four-
hour sampling time continued for the project duration.
As explained previously, the sludge handling system was sampled every
four hours when components were operational in order to conform to the
project's activity. It should be noted that raw sludge was sampled once for
each primary from which sludge was pumped and the supernatant once each time
the operation was performed. The filter backwash was sampled every time a
filter backwashed. An attempt was made to sample the grit daily, but only 11
samples were collected.
The sample bottles were washed, acid-soaked, rinsed, and air-dried before
each use. All bottles were labeled in the lab with the sampling location for
each use. Intermittent stream-sampling bottles were then bagged by stream and
later placed at a convenient pit to be filled by plant operators. The nine
mainstream bottles were labeled and bagged in a set for each sample. These
bags were dropped off at a central plant location, the Zimpro service building
basement, where operators did the sampling. The full bottles were put in a
56
-------
large plastic garbage can which was brought to Purdue about every other day.
Bottles used for the intermittent streams were also placed in the garbage can.
The person collecting each sample wrote the date and the time on the label
with a waterproof marker.
At Purdue, the bottles were sorted and a log of the samples kept. When
flow data were available, generally after about a one- or two-day lag, samples
were composited for analysis and the bottles emptied and washed. There was
about a ten-day turnaround for the 1,000 sampling bottles used in the study.
Finally, the route taken by plant personnel for collecting the nine
mainstream processes had to be determined. Consulting with plant management,
a route was developed which minimized the distance and time spent sampling,
shown in Figure 9. All operators were familiarized with the route and had no
difficulty during the study. The same route was used for sampling the primary
influent.
Setting up a sampling program of this magnitude is a complex undertaking.
Careful attention must be paid to detail, particularly to obtain a truly
representative sample without undue inconvenience to people involved.
RESULTS
As stated previously, this field investigation at the Kokomo plant had
two purposes: First, to determine a complete mass balance of five selected
heavy metals (cadmium, chromium, copper, nickel, and zinc) and a shorter-term
mass balance for iron and lead; and. second, to actually complete such a
sampling program at the Kbkomo treatment plant.
Flow Rates
Mass balance comprises two elements: metal concentrations and measured
flow rates. Average daily flow rates during the 60-day period are shown in
Figure 10. In some instances, three figures label one flow stream. Figures
in parentheses refer to the average flow rate of that stream for the number of
days that it was in use, and the other figure refers to the average flow of
that stream on a 60-day basis. Thus the total flow of that stream is
presented and meaningful comparisons can be made between streams that were in
use for different numbers of days. Values are also associated with the two
accumulation terms. Accumulation in the raw sludge holding tank is actually
negative; that is, there was a greater volume at the start of the project than
at its completion. The direction of the arrow labeling the stream indicates
this. It is shown as an influent stream, since the indicated volume was
introduced to the system during the study. The accumulation in the Zimpro
thickener is positive. This is indicated by the arrow labeling the stream as
one of the effluents from the system because the positive accumulation can be
thought of as being removed from the system as a whole to a fictional storage
tank.
Table 27 summarizes recovery of the hydraulic balance. This can be
measured in two ways: percentage of difference between total influent and
total effluent quantities or pecentage of total influent accounted for in
57
-------
Aerators
Aerators
A Bottle pick-up
point, beginning
and end of sam-
pling route.
Grit chamber
Parshair
flume
Service
bidg.
influent M.K
Figure 9. Plant personnel sampling route.
58
-------
3Mt
17.4
en
10
) 17.6 *
Legend;
GRIT
CHAM.
(A/B)
C
1
P\
T-eAiy 22.3 T
0
A -Average Flow Rale when
PRIM-
SET
.0054
4C
0.189
i
1
i
RAW
SLUO
HOLD
Bs Number of days stream
in use
60 -da
00.078949)
l
, 1
ZIM
SYS
(0.116/39.5)
O.O760
\
AERATOfl
36.9
SEC. GRAV.
SE1> 18.8* FILT »7.1
10.0129/2)
0.00032
, 0.00375
i _ | . ___ . ^.
1 r-
(0.116/39.5)
0.0760
ZIM.
THICK
O.Q055
1
VAC.
FIL. ^
(37900 /dc
(0.0287/32.5) 20500
O.OI55
0.0825/34) (0.024/32.5)
U.UnoO f. «!»
U. UI3
ALL VALUES ARE IN MILLION GALLONS PER DAY UNLESS OTHERWISE INDICATED
Figure 10. Hydraulic balance.
-------
TABLE 27. SUMMARY OF HYDRAULIC BALANCES
Operation'"
MP 1
Grit Chamber
MP 2
Primary Settler
MP 3
Aerators
Secondary Settlers
Gravity Filters'
Raw Sludge Holding Tank
Zimpro System
Zimpro Thickener
Vacuum Filters
Influent
Total Flow
(MGD)
17.5
17.6
23.3
23.3
39.9
40.1
36.9
18.8
0. 194
Q.076
0.076
0.0158
Effluent
Total Flow
(MGD)
17.6
17.6
22.3
22.4
40. 1
40.6
37.2
18.7
0.156
0.076
0.0716
0.0145
% Recovery
101
100
95.7
100
101
101
101
99.7
80.3
100
14.1
91.6
total effluent. The two methods are essentially equivalent, but the latter
method was chosen and is termed "percent recovery." Table 27 shows that the
mainstream operations have very good hydraulic balances and that the sludge
stream operations are somewhat poorer.
Metal Concentrations
The second important component of mass balance is the concentration of
heavy metal at various points within the treatment plant. Concentration is
also important because it must be reduced to an acceptable level for discharge
and it limits the land application rate of the sludge.
Tables 28 through 38 show concentrations of each metal at various points
within the treatment plant. Only major streams are identified; the main
streams are listed in Table 39. In addition to data for each unit operation
of the plant, there are data for the plant as a whole and for each of the two
components of the activated sludge system. Figures 11 through 17 are specific
for each metal and show its concentration profile through the plant. The
tables show the percent removal or the concentration, or both, of each metal.
.60
-------
TABLE 28. CONCENTRATION OF HEAVY METALS AROUND THE ENTIRE TREATMENT PLANT
Plant Inf. (Avg.)
(Range)
Plant eff. (Avg.)
(Range)
Sludge Cake1 (Avg.)"
(Range)
Percent Removal
Cd
0.0328
0. 001 92-
0.0929
0.00631
0.0005-
0.0770
377
165-
600
80.8'
Concentration (mg/1)
Cr Cu Ni Zn
0.786
0.0267-
5.33
0.0167
0.00391
0.0727
1060
518-
4250
97.9
Concentration
Fe Pb
Plant Inf. (Avg.)
Plant Eff. (Avg.)
Sludge Cake1 (Avg.)
Percent Removal
17-3
0.335
71900
98.1
0.0507
0.00255
94.0
95.0
0.168
0.0558-
0.785
0.0252
0.00966-
0.0754
1790
702-
6650
85.0
(mg/1)
SS
151
7.8
394000
94.8
0.115 2.07
0.0107- 0.379-
0.485 5.52
0.0812 0.233
0.0303- 0.0721-
0.177 1.05
533 '13600
215- 4820-
968 17400
29.4 88.7
1 Sludge Cake concentration expressed in terms of mg/kg on a dry weight
basis.
61
-------
TABLE 29. CONCENTRATION OF HEAVY METALS AROUND GRIT CHAMBER
Grit Chamber Inf. (Avg.)
(Range)
Grit Chamber Eff. (Avg.)
(Range)
Grit1 (Avg.)
Percent Removal
Cd
0.177
0.0135-
0.7^8
0.177
0.130-
0.786
124
0.0
Concentration (mg/1)
Cr Cu Ni Zn
0.864
0.175-
2.85
0.931
0.200-
1.78
344
-7.8
Concentration
Fe Pb
Grit Chamber Inf. (Avg.)
Grit Chamber Eff. (Avg.)
Gritl
Percent Removal
91.4
91.7
175
-0.3
0.282
0.261
1.55
7.4
0.841
0. 111-
4.25
0.705
0.0988-
3.20
1080
16.2
(mg/1)
S3
-----
451
0.437 5.60
0.0660- 1.16-
5.49 1.21
0.471 5.42
0.0528- 1.27-
8.18 27.4
465 ' 4610
-7.8 3.2
-
1 Grit concentration expressed in terms of mg/kg on a dry weight basis
62
-------
TABLE 30. CONCENTRATION OF HEAVY METALS AROUND PRIMARIES
Concentration (mg/1)
Pri. Inf. (Avg.)
(Range)
Pri. Eff. (Avg.)
(Range)
Raw Sludge (Avg.)-
( Range")
Percent Removal
Concentration Factor
Cd
0.425
0.0793-
1.06
0.251
0.0397-
0.772
33.3
10.2-
57.3
40.9
138
Cr
2.19
0.430-
5.86
1.33
0.181-
3.59
102
29.8-
171
39.3
119
Concentration
Pri. Inf. (Avg.)
Pri. Eff. (Avg.)
Raw Sludge (Avg.)
Percent Removal
Concentration Factor
Fe
156
50.1
13600
67.9
128
Pb
0.684
0.125
30.7
81.7
54.9
Cu
2.18
0.408-
6.35
1.15
0. 124-
3.83
143
61.5-
314
47.2
139
(mg/1)
S3
483
____
Mi
1.20
0.286-
3.64
0.615
0.0478-
2.38
65.8
18.7-
368
48.8
112
Zn
15.8
2.81-
44.3
8.42
1.04-
28.3
- 965
"366-
2360
46.7
131
63
-------
TABLE 31. CONCENTRATION OF HEAVY METALS AROUND AERATORS
Aer. Inf. (Avg.)
Aer. Eff. (Avg.)
WAS-R (Avg.)
Cd Cr
1.36 7.17
1.35 7.16
1.85 8-06
Concentration (mg/1)
Cu Ni Zn Fe Pb
5.79 2.76 46.4
5.79 2.75 46.3
8.29 3-92 67.5
468 1.23
518 1.22
570 1.21
SS
4760
4760
4760
TABLE 32. CONCENTRATION OF HEAVY
METALS AROUND SECONDARIES
_
Aer. Eff. (Avg.)
(Range)
Sec. Eff. (Avg.)
(Range)
RAS (Avg.)
(Range)
Cd
1.35
0.579-
2.50
0.0124
0.00119-
0.121
2.50
0.605-
6.95
Concentration (mg/1)
Cr Cu Ni
7.16 5.79
2.88- 3.02-
12.6 10.2
0.0773 0.0574-
0.0153- 0.0103-
0.863 0.543
11.0 11.6
4.27- 3.89-
33.1 27.4
2.75
0.432-
6.36 _
0.0988
0.0419-
0.360
4.74
0.742-
15.6
Zn
46.3
" 14.1-
109
0.488
0.133-
3.79
86.3
17.7-
224
Concentration (mg/1)
Fe Pb SS
Aer . Eff . ( Avg . )
Sec. Eff. (Avg.)
HAS (Avg.)
518
1.75
837
1.22 4760
0.00525 26.3
1 . 95 8720
64
-------
TABLE 33. CONCENTRATION OF HEAVY METALS AROUND ACTIVATED SLUDGE SYSTEM
Pri. Eff. (Avg.)
(Range)
Sec. Eff. (Avg.)
(Range)
WAS-R (Avg.)
(Range)
Percent Removal
Concentration Factor
Cd
0.251
0.0397-
0.772
0.0124
0.00119-
0.121
1.85
0.385-
3.93
95.1
7.75
Concentration (mg/1)
Cr Cu Ni
1.33
0. 181-
3.59
0.0773
0.0153-
00.863
8.06
2.01-
15.0
94.2
6.43
1.15
0. 124-
3.83
0.0574
0.0103-
0.543
8.29
1.42-
18.3
95.0
7.59
0.615
0.0478-
2.38
0.0988
0.0419-
0.360
3.92
0.440-
7.55
83.9
7.59 _-
Zn
8.42
1.04-
28.3
0.488
0.133-
3-79
67.5
18.7-
1.26
94.2
8.51
Concentration (mg/1)
Fe Pb SS
Pri. Eff. (Avg.)
Sec. Eff. (Avg.)
WAS-R (Avg.)
Percent Removal
Concentration Factor
50.1
1.75
570
96.5
11.8
0.125
0.00525
1.21
95.8
10.1
483
26.3
4760
94.6
10.4
65
-------
TABLE 34. CONCENTRATION OF HEAVY METALS AROUND GRAVITY FILTERS
Sec . Eff
. (Avg.)
(Range)
Plant Eff. (Avg.)
(Range)
Filter B
Percent
.W. (Avg.)
(Range)
Removal
Cd
0.0124
0.00119-
0. 121
0.00631
0.0005
0.0770
.259
0.00192-
0.516
49. 1
Concentration (mg/1)
Cr Cu Ni In
0.0773
0.0153-
0.863
0.0167
0.00391
0.0727
1.03
0.0493-
3-90
78.4
Concentration
Fe Pb
Sec. Eff
. (Avg.)
Plant Eff. (Avg.)
Filter B
Percent
.W. (Avg.)
Remov al
1.75
0.335
35.4
80 .-9
0.00525
0.00255
0.0803
51.4
0.0574 0.0988 0.488
0.0103- 0.0419- 0.133-
0.543 0.360 3-79
0.0252 0.0812 0.233
0.00966- 0.0303- 0.0721-
0.0754 0.177 1.05
0.460 0.441 0.410
0.00557- .0425- 0.215-
2.18 1.58 17.6
56.1 17.8 52.3
(mg/1)
S3
26.3
7.8
440
70.3
TABLE 35. CONCENTRATION OF HEAVY METALS AROUND RAW SLUDGE HOLDING TANK
Concentration (mg/1)
Cd Cr Cu Ni Zn Fe
Pb
TS
Raw Sludge (Avg.) 24.0 102 143 56.8 965 13600 30.7
Urn. Feed (Avg.) 21.0 71.5 99.9 39.9 745 9630 23-1 68600
Sup. (Avg.) 28.4 85. 140 53.0 889 15100 36.9 3000
66
-------
TABLE 36. CONCENTRATION OF HEAVY METALS AflOUND ZIMPRO REACTOR
Concentration (mg/1)
Cd Cr Cu Mi .Zn Fe Pb TS
Zim. Feed (Avg.) 21.0 71.5 99.9 39.9 745 9630 231 68600
02 Sludge (Avg.) 19-9 68.9 67.2 38.1 720 9910 24.0 61000
TABLE 37. CONCENTRATION OF HEAVY METALS AROUND ZIMPRO THICKENER
Concentration (mg/1)
Cd Cr Cu Mi Zn Fe Pb SS
Op Sludge
(Avg.) 19.9 68.9 67.2 38.1 720 9910 24.0 61000
V.F. Feed
(Avg.) 54.3 200 244 91.1 1730 20400 51.4 159000
Zim. Sup.
(Avg.) 1.18 4.42 5.24 2.87 35.. 7 181 0.469
Concentration
Factor 2.73 2.90 3.63 2.39 2.40 206 2.14 2.61
67
-------
TABLS 38. CONCENTRATION OF HEAVY METALS AROUND VACUUM FILTERS
Concentration (mg/1)
Cd Cr Cu Mi Zn Fe Pb TS
V.F. Feed
(Avg.) 54.3 200 244 91.1 1730 20400 51.4 159,000
Filter Cake1
(Avg.) 377 1060 1790 533 13600 71900 94.0 394,000
Filtrate
(Avg.) 25.6 72.8 146 66.4 1014 21900 33-0 56200
Concentration
Factor 6.94 5.30 7.3 5.85 7-86 3.52 1.83 2.48
1 Filter Cake concentration expressed in terms of mg/kg on a dry weight
basis.
TABLS 39. CONCENTRATIONS OF HEAVY METALS IN MINOR PLANT STREAMS
Concentration (mg/1)
Stream Cd Cr Cu Ni Zn Fe Pb
Primary Skimmings 0.350 1.42 3.27 1.33 7.70
Secondary
Skimmings 0.0772 0.446 0.556 2.05 6.88
WAS-U 1.18 7.43 6.88 3.27 52.0
Zim. By-Pass 19.2 41.7 81.0 26.7 510
Lagoon Feed 54.3 200 244 91.1 1730
Raw Sludge Holding
Tank-Accumulation 28.4 85.0 140 53-0 889
Zimpro Thickener-
Accumulation 54.3 200 244 91.1 1730
68
-------
CApMIUM CONCENTRATION (g/kg)
en
§
13
H
O
H.
H-
M
n»
PL. INF
6R.CH
INF
GR.CH
EFF.
PR I. INF
PRI.EFF
AER.EFF
SEC.EFF
PL .EFF
RAW SL
2IM FEED
V.F. FEED
CAKE
P
g
-L.
p
4-
o
-f-
o
o
o
o
o
o
-------
CHROMIUM CONCENTRATION (rng/kg)
(D
*vj
o
o
H-
H
n>
PL.INF
6R.CH
INF
GR.CH
EFF
PRI
INF
PRI
EFF
AER.EFF
SEC.EFF
PL .EFF
RAW.SL
ZIM.FEEO
V.F. FEED
CAKE
p
T
o
-4-
o
o
o
o
o
o
o
o
-------
COPPER CONCENTRATION
is
g PL. INF.
H
GR.CH.
£ INF
g £ PR!. INF
it n>
ft 0
^ ^ PRIEFF
i-* n
Pi o
rt*g . AER.EFF
W H
rt
H 0
g § SEC. EFF
§ n
U flt
' S PL. EFF
H
rt
H-
w RAWSL
H-
£ Z1MFEED
H
H-
c V.F FEED
CO
CAKE
o 8
? f i f ? f ,
1 1 r l r ^
i ,
\
-------
NICKEL CONCENTRATION (mg./kq)
n
»
o
PL.INI:
6R.CH-
INF
6R.CH.
EFF
PR I, INF
PRI. EFF
AER.EFF
SEC. EFF
PL. EFF
RAW. SL
ZIM FEED
V.F. FEED
CAKE
£
o
o
o
I
-------
ZINC CONCENTRATION (mg./kg)
CO
ID
tl
n
o
H»
P
(0
PU.INF
6R.CH
INF
GR.CH
EFF
PR I. INF
PRIEFF
AER. EFF
SEC. EFF
PL.EFF
RAW SL
ZIM FEED
V-F. FEED
CAKE
b
o
o
8
o
o
-------
en
H
o
O
o
Hi
H-
PL. INF
GR.CH
INF
GR.CH
EFF
PRI.INF
PRLEFF
AER.EFF
SEC EFF
PL. EFF
RAW SL
ZIM FEED
V.F. FEED
CAKE
IRON CONCENTRATION (mg./kft) 5 O
- - 0 O ° O
0 O O O O O
- 1 | 1 i I ^
1 1 -I I « W*
1
\
-------
1000-t
100-
5 !0-
6»
ZT
2
-
£ i-o-r
K, I
1-
2.
U
5
o
Q 0.1-
u
_J
0.01-
*
I
t X xu. u_ u. u. u.
-. °- i °- i - & & i
a! o O 5 -
a. cc Oi o
0- UJ UJ
< en
u.
u.
UJ
.
a.
-
-J a a
en uj uj m
UJ UJ ^
5 u, u. <
2 2 u: °
M >
Figure 17. Lead profile.
75
-------
The concentration factor is defined by Olthor (1978) as the sludge
concentration divided by the differences between the influent and effluent
metal concentrations, but for sludge handling streams, it is merely the
effluent dividied by the influent metal concentrations.
Examination of data in Tables 28 to 38 and Figures 11 and 17 reveals
several important points. The most striking feature is the similar behavior
of all the metals except nickel. All except nickel are removed to a very
large extent in the mainstream operations and are concentrated in the filter
cake. The percent removal calculated in the tables can be somewhat
misleading. As used, they are defined to be the percent removal with respect
to the influent anrd effluent o_f the process considered. This method of
expressing removal efficiencies is necessary because of on-plant
recirculation. For example, if the percent removal of primaries was
calculated on the plant influent, a negative percent removal would result,
which would give no useful information about that system's efficiency.
Table 29 shows that the grit chamber is largely ineffective for heavy
metals removal, as would be expected. The negative removals measured for
chromium, nickel, and iron are considered insignificant, in effect, zero. As
seen, the concentrations of metals in grit is fairly high, necessitating some
consideration of its" ultimate disposal. The aerated grit chamber at Kokomo
produces a grit that has a great deal of putrescible organic matter associated
with it. This organic matter originates from recirculating three of the
sludge streams to the set well preceding the grit chamber. This matter raises
the metal concentration of grit chamber influent and effluent over plant
influent. It seems logical that eliminating this meter from the grit would
reduce the metal levels and help the odor problem. Adjusting _the air flow
rate in the grit chamber might also help. *"
The removal efficiency of the primaries for the seven metals is
approximately 50 percent, shown in Table 30. Iron and lead are somewhat
higher and chromium somewhat lower. The large iron removal may be from its
propensity to act as a coagulant, especially realizing that the Kokomo plant
wastes its excess secondary sludge to the primaries and noting the high iron
concentration with which it mixes, 91.7 mg/1, in the grit chamber effluent.
The lead value is probably due to the low concentration of lead measured and
the relative insensitivity of atomic absorption spectrophotometry to lead.
The lower chromium removal may be due to the high solubility of chromium VI
present in the influent. The concentration factor regarding sludge mirrors
the trends of the percent of removals, however, the discrepanncy in lead is
opposite to that of the percent of removal, that is, if more lead were removed
than the average, its concentration factor should be higher than the average.
It is lower. This supports the reasoning of experimental error in
determination of low lead values. Unfortunately, Kokomo does not report
suspended solids of the true primary influent but actually of the grit chamber
effluent, so no comparison could be made of heavy metals to suspended solids
removal in the primaries.
Table 33 shows that the activated sludge system is the primary removal
operation for heavy metals. The removal efficiencies of all the metals,
excepting nickel, are about 95 percent. The lower nickel removal efficiency
76
-------
(83.9 percent) is due to its inherent chemistry and has been observed by many
others, as shown in the literature review. At this point, metal
concentrations have decreased from the influent concentration to the plant.
They have been concentrated by a factor of about 7 in the mixed liquor. The
removal efficiency of the secondary clarifier is very high for suspended
solids and metals, shown in Table 32. In fact, the removal efficiency of
suspended solids mirrors that of heavy metals; however, no generalizations are
possible due to different removal mechanisms for suspended solids and metals,
for example, floe enmeshment versus adsorption onto the floe.
Gravity filters remove suspended solids. At Kokomo, filters remove 70.3
percent of the suspended solids but only about 50 percent of cadmium, copper,
zinc, and lead. Chromium and iron are removed to about the same degree as
suspended solids, while nickel is barely removed. Since some insoluble metal
is removed by secondary clarifiers, influent to the filters should contain a
higher proportion of soluble metal, and thus the filters should not be as
effective for metal removal as for suspended solids removal. This is borne
out by most of the metals, in particular nickel, but not for chromium and
iron. This could possibly mean that the majority of the iron and chromium are
present in insoluble form.
The sludge-handling stream increases metal concentration to that of
filter cake. However, as shown in Table 35, no increase occurs through the
raw sludge holding tank, in fact, metal concentration decreasess. The reason
may depend on the piping in the tanks which are old anaerobic digesters and
therefore do not act as thickeners, since only minor modifications occurred in
the changeover to holding tanks.
There is no concentration through the Zimpro reactors, shown in Table 36.
This is expected, as well as the slight decrease in solids volatilized by the
process. The concentration is effected by the thickener which results in a
twofold or threefold concentration of all metals and solids, with a purely
thickening phenomenon occurring. The Zimpro supernate also has low metal
levels.
Metal concentration is continued by vacuum filters, this time with about
a five to sevenfold increase. Solids do not quite mirror this increase
because cake metal content is expressed on a dry solids basis, while the
solids content of cake is on a wet-weight basis. Dividing the concentration
factor for the solids by 0.40, about the average percentage of solids,
increases it to 6.2, which is in the same range as the metals.
Tables 28 through 3^ present ranges in metal concentrations, as well as
averages. These are presented primarily for the sake of completeness and to
demonstrate that the plant operated during periods of high and low metal
loadings, and that the metal concentration at points within the plant is not
static but varies greatly.
Comparison of Table 28, the metal concentrations at Kokomo, with those of
other cities in Table 7 shows that Kokomo has very high influent cadmium and
iron concentrations, moderately high chromium and zinc concentrations, normal
copper and nickel levels, and low lead levels. However, removal efficiencies
77
-------
of the Kokomo plant are, except for nickel, better than any of the other
treatment plants of Table 8. Also effluent metal concentrations at Kokomo are
slightly lower than most plants listed in Table 9. These facts substantiate
hypotheses of heavy metal removal by insoluble iron oxides as one of the major
removal mechanisms, as suggested in the literature review. Comparison of
sludge data from Kokomo to that from other cities shows that Kokomo has high
sludge metal concentrations and that, in particular, cadmium and zinc are very
high.
The Mass Balance
The total poundage of a given metal which passes through any stream
during the 60-day period is the product of the flow rate and concentration.
Mass balances determined about each of the nine operations of Figure 7, as
well as the three mixing points and plant, are shown in Tables 40 through 52,
which should be used in conjunction with Figure 7. Percent of recovery is
again used as a measure of mass balance and is the same concept used earlier
for flow rates. Figures 18 through 24 are specific to each metal for the
treatment plant and its operations. The mass balance data are complete for
the five principal metals studied, but they only include mainstream operations
for iron and lead because of the short sampling period of 11 days, which did
not allow enough sampling for a meaningful evaluation. Table 53 summarizes
the percent of recovery of each metal from each unit operation.
The usefulness of a mass balance is that it shows the fate of a
particular metal as it moves through a system such as a treatment plant. The
fraction of influent metal present in the sludge should be theoreticaly equal
to the removal efficiency of a process for the metal. Table^.54 contains
results for the primary clarifiers and plant as a whole. The removal
efficiency of the primaries is based on the primary influent; the filter cake
is actually a sum of the lagoon feed plus the filter cake. The second purpose
of a mass balance is to locate potential errors in analyses of metal
concentration, or flow rates.
A comparison of Table 54 to Table 30 shows good agreement between removal
percentages and the fraction of influent metal in the sludge for the
primaries. Comparison of Table 54 with Table 28 does not show such good
agreement for the plant as a whole because of errors in concentration or flow
rates of the mass balance. Examination of Table 53 for the entire plant
reveals that same data trend, as does Table 54. This indicates that cadmium,
copper, and nickel values are realistic, since they do no greatly differ from
the removal percentages in Table 28. The percent of zinc recovery is
relatively low, indicating a possible error in measuring the zinc
concentration of the filter cake. This is possible because of the great zinc
concentrations measured which necessitated dilutions of up to 10,000:1 in some
instances, thus greatly increasing the chance for experimental error.
However, the percent of recovery of zinc about the vacuum filters is close to
100 percent, seemingly invalidating the previous argument. A closer data
examination reveals a low (80.7) percent of recovery, indicating that the zinc
concentration in the feed to the vacuum filter is also wrong, possibly for the
same reasons. In summary, the actual zinc concentration in the vacuum filter
feed and in the filter cake is low due to experimental error,
78
-------
TABLE 40. MASS BALANCE AROUND THE PLANT AS A WHOLE
Streams
Plant
Inf.
Raw SI. Hold.
Tank Ace.
TOTAL IN
Plant
Filter
Lagoon
Ziaipro
Ace.
Grit
TOTAL
Eff.
Cake
Feed
Thickener
OUT
% Recovery
Cd
285
64.5
350
54-. 9
186
102
149
4.3"
496
142.0
Cr
6848
274
7122
145
525
283
551
11.9
1516
21.3
Pounds of Metal
Cu Ni Zn
1460
384
1844
220
880
459
671
37.3
2267
123-0
1003
177
1180
707
260
171
251
16.1
1405
119. 1
18019
2591
20610
2026
6691
3249
4756
160
16882
81.9
Fe '
26442
680
27122-_
515
6495
0
0
1310
8320
«
Pb
77.8
1.7
79.5
3.9
8.5
0
0
11.6
24.0
*
* Note: insufficient sampling period for balance.
79
-------
TABLE 41. MASS BALANCE AROUND THE GRIT CHAMBER
Streams
Gr . Ch . Inf .
TOTAL IN
Gr . Ch . Ef f .
Grit
TOTAL OUT
% Recovery
Cd
1542
1542
1540
4.3
1544
100.1
Cr
7530
7530
8102
11.9
8114
107.8
Pounds of Metal
Cu Mi Zn
7320
53200
6139
37.3
6176
84.4
3804
3804
4101
16.1
4117
108.2
48775
48775
47255
160
47415
97-2
Fe
140220
140220
140696
1310
142006
101.2 "
Pb
432
432
401
11.6
413
95.5
TABLE 42. MASS BALANCE AROUND THE PRIMARIES
Streams
Cr
Pounds of Metal
Cu Ni Zn
Fe
Pb
Pri. Inf. 4738 24482 24301 13422 175781 303440 1328
TOTAL IN 4738 24482 24301 13422 175781 303440 1328
Pri. Eff. 2785 14837 12735 6334 93571 96490 242
Raw SI. 2272 9656 13561 6227 91310 234810 531
TOTAL OUT 5057 24493 26296 13061 184881 331300 773
% Recovery 106.7 100.0 108.2 97.3 105.2 109.2 58.2
80
-------
TABLE 43. MASS BALANCE AROUND THE AERATORS
Streams
Aer . Inf .
TOTAL IN
WAS-R
Aer . Eff .
TOTAL OUT
% Recovery
Cd
27279
27279
1736
25015
26751
98.1-
Cr
143821
143821
10952
132215
143167
99.5
Pounds of Metal
Cu Ni In
116139
1161-39
10130
106830
116960
100.7
55376
55376
4810
50772
55582
100.4
930542
930542
76651
854792
931443
100.1
Fe
1551900
1551900
183100
1397000
1580100
101.8
Pb
4074
4074
386
3668
4054
- 99.5
TABLE 44.
MASS BALANCE AROUND THE
SECONDARY
CLARIFIERS
Streans
Aer. Eff.
TOTAL LN
HAS
WAS-U
Sec. Eff.
TOTAL OUT
Cd
25015
25015
22118
1656
117
23891
Cr
132215
132215
97141
3842
727
101710
Pounds of Metal
Cu Ni Zn
106830
106830
102643
5091
540
108274
50772
50772
42015
2405
929
45349
854792
854792
764275
47306
4590
816171
Fe
1397000
1397000
1389000
2839
1392000
Pb
3668
3668
3234
8.5
3242
% Recovery 95.5 76.9
101.4 89-3
95.5
99.7
5.4
81
-------
TABLE 45. MASS BALANCE AROUND THE GRAVITY FILTERS
Streams
Sec . Ef f .
TOTAL IN
PI. Eff.
Filter B.W.
TOTAL OUT
% Recovery
Cd
117
117
54.9
59.4
114
97.7
Cr
727
727
145
690
835
114.9
Pounds of Metal
Cu Ni Zn
540
540
220
308
528
97.8
929
929
707
295
1002
107.9
4590
4590
2026
2743
4769
103.9
Fe
2839
2839
515
3060
3575
125.9
Pb
8.5
8-5
3.9
7.0
10.9
128.2
-
TABLE 46. MASS BALANCE AROUND THE RAW SLUDGE HOLDING TANK
Streams
Cd
Pounds of Metal
Cr
Cu
Ni
Zn
Raw SI.
Raw SI. Holding
Tank Ace.
$ Recovery
2272 9656 13561 6227 91310
64.5 274 384
177 2591
TOTAL IN
Zim . Feed
Zim. By-Pass
Sup.
TOTAL OUT
2336
805
4.7
1122
1932
9930
2742
10.1
3356
6108
13945
3832
19.6
5535
9387
6404
1529
6.5
2092
3628
93901
28559
124
35102
63785
82.7 61.5 67.3 56.6 67.9
82
-------
TABLE 47. MASS BALANCE AROUND ZIMPRO REACTORS
Pounds of Metal
Streams Cd Cr Cu Mi Zn
Zln. Feed 805 2742
TOTAL IN 805 2742
02 Sludge 767 2641
TOTAL OUT 767 2641
% Recovery 95-3 96.3
3831
3831
2576
2576
67.2
1532 28560
1532 28560
1462 27598
1462 27598
95.4 96.6
TABLE 48. MASS BALANCE AROUND THE ZIMPRO THICKENER
-
Streams
02 Sludge
TOTAL IN
V.F. Feed
Zim. Sup.
Lagoon Feed
Zim. Thickener
Accumulation
TOTAL OUT
Cd
767
767
422
27.5
102
149
700
Pounds of Metal
Cr Cu Mi
2641
2641
1555
103
283
551
2492
2576
2576
1894
123
459
671
3147
1462
1462
708
67.2
171
251
1197
Zn
27598
27598
13436
835
3249
4756
2276
Recovery
91-3 94.4 122.2 81.9 80.7
83
-------
TABLE 49. MASS BALANCE AROUND THE VACUUM FILTERS
Pounds of Metal
Streams
V. F. Feed
Zim. By -Pass
TOTAL IN
Filter Cake
Filtrate
TOTAL OUT
% Recovery-
Cd
422
4.7
427
186
166
352
82.5
Cr
1555
10.1
T565
525
473
998
63.8
Cu
1894
19.6
1914
880
947
1827
95.5
Ni
708
6.5
714
261
432
693
97.1
Zn
13^36
125
13560
6691
6596
13287
98.0._
7ABLE 50. MASS
BALANCE
ABOUND
MIXING POINT
1
Pounds of Metal
Streams
PI. Inf.
Sup.
Zim. Sup.
Filtrate
TOTAL IN
Gr. Ch. Inf.
TOTAL OUT
Cd
285
1122
27.5
166
1550
1542
1542
Cr
6848
3356
103
474
10781
7530
7530
Cu
1460
5535
123
947
8065
7320
73200
Ni
1003
2092
67.2
432
3594
3804
3804
Zn
18019
35102
835
6596
60552
48775
48775
% Recovery
99.5 69.8
90.8
105.8
80.6
-------
TABLE 51. MASS BALANCE AROUND MIXING POINT 2
Pounds of Metal
Streams
Gr. Ch. Eff
WAS-R
WAS-U
Filter B.W.
TOTAL IN
Pri. Inf.
TOTAL OUT
J Recovery
Cd Cr
1541 8102
1736 10952
1656 38^2
59.4 690
4992 23536
4?38 24482
4738 24482
94.9 103.8
Cu
6139
10130
5091
308
21668
24301
24301
112.1
Mi
4101
4810
2405
295
11611
13421
13421
115.6
Zn
47255
76651
47306
2743
173955
175781
175781
101.0
Fe
140696
183100
0.0
3059
326855
303440
303440
92.8
Pb
401
386
O.C
7.0
794
401
401
50.5
TABLE 52. MASS BALANCE AROUND
MIXING
POINT 3
«
-
Pounds of Metal
Streams
Pri. Eff.
HAS
TOTAL IN
Aer . Inf.
TOTAL OUT
Cd Cr
2785 14837
22118 997141
24903 111978
27279 143821
27279 143821
Cu
12735
102643
115378
116139
116139
Ni
6834
42015
48849
55376
55376
Zn
93591
764275
857866
930542
930542
Fe
96490
389356
1485846
1551900
1551900
Pb
24200
3234
3476
4074
4074
J Recovery 109.5 128.4 100.7 113.4 112.0 104.4 117.2
85
-------
oo
286 'V
J
J 1542
4.3
GRIT-
CHAM.
1
1540 *vl
ALL VALUES ARE Ibs.
^4738 *
64.5
PRIM
SET
RAV
SLU
HOL
j
* i
22118
K
fe.
2785 ^^27279 '
2272
r *~*
i
^
.
a
1
805
ZIM
SYS.
1122
\
i
r
1735
\
AERATOR
4.7
767
25015
1655 59.4
SEC. GRAV
St
r~ ~
149
ZIM
THICK
1 ||7 " FILT 54.0
-» 102
VAC 186 __
422 FIL
27.5
166
Figure 18. Cadmium mass balance.
-------
CO
11.9
6848
97HJ
10952
3842
690
.X 7530
GRIT.
CHAM.
ALL VAluES IN Ibi.
N
,y24482*
274
PR
bt
RAV
SLL
HOL
IM
T-
Vi
2785 'Vi/27279 '
9656
1
1
V
10
.0
_J
2742
AERATOR
25OI5
10.1
ZIM.
SYS.
2641 '
3356
551
ZIM.
THICK.
SEC GRAV
" 14*
IZ"1 _283
L.
VAC.
1555 FIL. 525
IO3 473
Figure 19. Chromium mass balance.
-------
37.3
1460
oo
00
102643
10130
25091
3O8
12O
GRIT
CHAM
,/M
-X 2 4301
PRIM
SET
384
fc\
l2735~V?_y (16139
13561
«
I
RAW
SLUO
HOLD
ALL VALUES ARE lb$.
i
1
__J
3832
5535
\
ZIM
SYS
AERATOR
106830
SEC ^ GRAV-
SET 540 FILT 22
196
, 459
2576
671
V, 1 y
ZIM.
THICK.
L»
VAC r
1894 F 1 L 88O
123 947
Figure 20. Copper mass balance.
-------
4610
2405
295
42013 /"" \
'00
L/3804
GRIT
CHAM
,/MI
4101 V?
ALL VALUES ARE Ibs.
P\ f
J 134 22 ^
177 *
PRIM.
SET.
RAV
SLU
HOL
\
./i
6834 V:
»P\
1^55376"
6227
Y.
0
.0.
1
1
-.J
1529
ZIM
SYS.
AERATOR
50772*
6.5
SEC. GRAV.
SET. 929 FILT. 70
1 I/I
VJy "
1462
2O92
251
ZIM
THICK
U
VAC.
708 FIL> 261
67.2 432
Figure 21. Nickel mass balance.
-------
76651
47306
2743
160
764275
18019
48775
GRIT
CHAM
./M
47255 V
ARE Its.
P\
1 »
.^175781
2591
PRIM
SET
A
9357 1 ' Vf
91310
RAW
SLUO
HOLD
351
\
i
1
28559
02
s
L/930542
AERATOF
854792
124
ZIM.
SYS
SEC QRAV
SET 4590 FILT 2O2*
| JCfU
27598
4756
ZIM
THICK
i
VAC
FIL 6691
835 6596
Figure 22. Zinc mass balance.
-------
3O59
vo
'ESTIMATED
ALL VALUES ARE Ibs.
231610
CAKE
6495
Figure 23. Iron mass balance.
-------
to
7.0
ESTIMATED
ALL VALUES ARE Its.
531
CAKE
8.5
Figure 24. Lead mass balance.
-------
TABLE 53- SUMMARY OF MASS BALANCES
Unit Operation
Mixing Point 1
Grit Chamber
Mixing Point 2
Primaries
Mixing Point 3
Aerators
Sec. Settlers
Grav. Filt.
Raw SI. Hold T.
Zim. Reactors
Zim. Thickener
Vacuum Filters
Plant
Cd
99.5
100. 1
94.9
106.7
109.5
98. 1
95.5
,97.7
82.7
95.3
91.3
92.5
142.0
Cr
69.8
107.8
103.8
100.0
128.4
99.5
76.9
114.9
61.5
96.3
94.4
63.8
21.3
Percent Recovery
Cu Ni Zn Fe Pb
90.8
84.4
112.1
108.2
100.7
100.7
101.4
97.8
67.3
67.2
122.2
95.5
123.0
105.8
108.2
115.6
97-3
113.4
100.4
89.3
107.9
56.6
95.4
81.9
97.1
119.1
80.6
97.2 101.2 95.2
101.0 92.8 50.5
105.2 109.2 58.2
112.0 104.4 117.2
100.1 101.8 99.5
95.5 99.7 88.4
103.9 125.9 -. 128.2
67. 9 m IL- _
96 . 6
80.7
98.0
81.9 * *
Note :. Insufficient
TABLE 54.
sampling
period
for balance.
FRACTION OF INFLUENT METAL IN
THE SLUDGE
Fraction of
Cd Cr
Primary Sludge
Filter Cake
0.48
1.01
0.39
0.12
Influent
Cu
0.56
0.91
1 Mass of Metal
Ni Zn
0.46 0.52
0.43 0.55
Based on primary influent and plant influent for primary
sludge and filter cake respectively. Mass in filter cake
sludge includes mass in lagoon feed also.
93
-------
The percent of recovery of chromium about the plan.t is also very low
because, first, the cake concentration is too low. The average concentration
reported as 1,060 mg/kg. The Kokomo lab has reported chromium levels of 3,000
to 4,000 mg/kg over the past year. The low percent of recovery of chromium
about the vacuum filters (63-8 percent), with no correspondingly low value
about the Zimpro thickener, as in zinc, also points to the error in chromium
concentration in the filter cake. This error probably arises for the same
reason as did the zinc error, i.e., the excessively high dilutions needed for
chromium in the filter cake, 1,000:1. However, the measured chromium
concentration in the sludge ranged from 207 to 541 mg/kg on a wet-weight
basis, with an average of 426 and standard deviation of only 66 mg/1, which
would indicate consistent analytical results. Second, the high concentration
of chromium in the plant influent is a problem. The mass balance about mixing
point 1 bears this out (69-8 percent recovery). This high value was largely
due to a spike of 5-33 mg/1 chromium received by the plant on Day 55. This
was one of the days that a profile of the influent metal as a function of time
was done. If a large spike entered the plant for a short period at the time
that a sample was collected, that concentration was assumed to be entering the
plant for a four-hour period. While this may be true of a typical sample, it
is not true, by definition, of a spike, so an actual average influent
concentration may be lower. Other extremely high values were reported on Days
21 and 3**.
Another discrepancy is the uniformly low percent of recoveries reported
for the raw-sludge holding tank which could be due to sampling problems or
errors in flow-rate measurement. Table 27 indicates that the hydraulic
balance only accounted for 80.3 percent of the influent flow which could
account for the percent of recoveries about the tank, shown in Table 46.
There possibly also were errors in sampling procedure siflce, if the
supernatant were not sampled at the operation's midpoint, as specified, but
rather near the start, an excessively dilute sample resulted.
The only other major data error for the five metals is the low percent of
recovery for chromium about the secondary clarifiers and the high percent of
recovery about mixing point 3- This arises from the same sourcea low
measured chromium concentration in the HAS. Since the other metals at these
points to not have this, it indicates an experimental error in chromium
determination.
The mass balances for iron and lead appear reasonable considering the
limited sampling period and relative insensitivity of AA toward iron and lead.
Patterns and Effects of Heavy Metals
Raw data generated during this project can be manipulated many different
ways, and used with lab data from the treatment plant, it can possibly
identify effects of heavy metals on the treatment process.
The daily mass of metal entering the plant is shown in Figures 25 to 30.
The periodic pattern of the day-to-day metal influent is the most striking
observation. Cadmium is the most pronounced in this regard. Sundays are
94
-------
o
to
O
O
o
o
20 -
15 --
10 -
(S)= Sunday
Days
S S
8-2 8-6
S S S
8-13 8-20 8-27
60
S S S S S
9-3 9-10 9-17 9-24 ICH
Figure 25. Influent cadmium loading Co plant during study.
-------
96
Chromium Loading (ibs./day)
cw
c
tt>
e
ft
9
rt
o
s
H-
i
o
a.
H-
oc
rr
O
O
C-
c
3
05
a
-------
VO
o
oo
in
O>
C
T3
O
O
_J
-------
VO
oo
o
^
l/j
0>
a
o
O)
j*:
o
10--
(61.6)
Days 8~6
S S S
8-20 . 8-27 9-3
S S S
9-10 9-17 9-24
60
S
10-1
Figure 28. Influent nickel loading to plant during study.
-------
(578) (665)
VO
tfl
cn
c
"-o
o
o
o
c
N 100--
200
(S)-Sunday
10
Days 8-6
S
8-13
S
-H 1 \ t
20 30
8-20 8-27 9-3
S S S
i , H-, H-
*0 I 50 I 60
9-10 9-17 9-24 10-1
S S S S
Figure 29. Influent zinc loading to plant during study.
-------
O>
o O
0 o
c
o
4000 --
3000-
2000-
(8520>/L *
"20
-15
1000 -
Days 35
W
Dates 9-6
--10
.a
TJ
o
O
T3
O
a>
Figure 30. Influent iron and lead loading to plant during study.
-------
identified with "S" on each graph, and show the mass of influent metal drops
significantly on weekends, which would indicate an industrial source for
metals. Also, on Day 33. a Labor Day Monday holiday, the heavy metal level
entering the plant was essentially the same as a Sunday. Generally, Saturdays
were also low, but not as low as Sundays because there probably was some
industry activity. Cadmium has the most regular pattern, and chromium the
most variable. The daily influent metal can vary from over 900 Ibs to under
10 Ibs in a week. Copper has the least regular pattern which might point to
significant copper sources other than industry, such as domestic or
runoff/infiltration. Although data were collected for only 11 days, iron and
lead had low Sunday inputs.
. The low Sunday inputs are not due to the lower flow rate over the
weekends because the average flow Monday through Friday was 16.6 mgd, while
Saturday and Sunday was 14.5 mgd, hardly the 40- to 50-fold difference in
metal loadings for these periods. Unlike low period regularity, peak leadings
showed irregularity, for example, peaks in cadmium concentration occurred on
Wednesday, Monday, Wednesday, Monday, Thursday, Thursday, Friday, and Friday
during successive weeks.
A limited study-examined the diurnal variation of the metals on Days 55,
56, and 57 for each influent sample without compositing. Figures 31 and 32
contain results and again reveal some very interesting patterns. Each metal
has a pattern of regularity, but the peaks and valleys occur at different
times. Cadmium and zinc peak in the morning, nickel and copper in the early
afteVnoon, and chromium in the early morning. With a sewer system as large as
Kokomo's, it is difficult to determine exact discharge time because the
different sources are located at varying distances from the treatment plant.
The data show discharge characteristics of industrial sources'rather than
domestic. The maximum hourly flow recorded during this three-day period was
28.3 mgd; the lowest, 12.4 mgd.
The Kokomo plant uses a Zimpro system and vacuum filters to process
sludge, so the data were analyzed for significant effects from these systems
on metal loading in the treatment plant. Table 55 shows this analysis under
several designations: /
(1) the average condition,
(2) with either the vacuum filter or Zimpro on-line,
(3) when neither in on-line,
(4) when both are on-line,
(5,6) when each is on-line regardless of the other, and
(7,8) when only each one is on-line.
The grit chamber influent was the influent metal concentration, as this was
the first sampling point downstream from where the Zimpro supernatant and
vacuum filter filtrate combine with plant influent. As columns 1 to 3 show,
the sludge handling systems have no consistent effect on metal loading. In
fact, the data indicate that no combination of systems has an effect. The
primary effect of sludge handling systems increases the effluent biochemical
oxygen demand (BOD) and primary effluent suspended solids. The frequency of
101
-------
o
*-
0>
t/)
TJ
C
> ZJ
O
CL
A
1
Tues.
p
Day
1
55
'A
Wed.
I'P 1
Day 56
A
Thurs.
7p-
Day
57
T
h*.
Days
Figure 31. Diurnal variation of Influent Cd, Cu, and Ni.
-------
e
o
k_
-C
o
o
Ul
T3
C.
n
o
Q_
--I20
Tues. Day 55
IP
Wed. Day 56
Dbys
Thurs. Day 57
Figure 32, Diurnal variation of Influent Cr and Zn.
-------
TABLE 55. EFFECTS OF ZIMPRO SYSTEM AND VACUUM FILTERS ON METAL LOADING AND
TREATMENT EFFICIENCY
Quantity
Flow mgd
Days Oper.
Cd Loading
Ong/1)
Cd in Eff.
Cr Loading
Ong/1)
Cr in Eff.
Cu Loading
Ong/D
Cu in Eff.
Ni Loading
Ong/D
Ni in Eff.
Zn Loading
Ong/1)
Zn in Eff.
Plant Eff. BOD
Ong/1)
Plant Eff. SS
Ong/1)
Sec. Eff. BOD
Ong/1)
Sec. Eff. SS
Oag/1)
Raw Sludge Flow
Cmgd)
Filter B.W.
Flow (mgd)
Pr. Eff. SS
(rng/1)
(1)
Avg.
17.4
60
0.177
0.00631
0.864
0.0167
-
0.841
0.0252
0.437
0.0812
5.60
0.233
30.8
7.7
32.0
26.1
0.189
1.10
617
(2)
V.F.
and/or
Zimpro
18.0
41
0.147
0.00673
0.843
0.0160
0.279
0.0264
0.437
0.0849
5.33
0.232
33.8
7.7
34.9
28.5
0.190
1.26
647
(3)
Neither
16.0
19
0.249
0.00533
1.01
0.0185
1.33
0.0225
0.437
0.0728
6.25
0.237
24.4
7.7
25.1
20.3
0.187
0.67
546
(4)
V.F. (5) (7) (8)
and Vac. (6) V.F. Zim.
Zinrpro Filter Zimpro Only Only
19.0 17.3 17.9 16.2 16.2
33.5 33.5 32.5 6.5 6.5
0.158 0.156 0.154 0.165 0.0914
0.00554 0.00479 0.00538 0.00693 0.0107
0.876 0.844 0.886 0.959 0.538
0.00823 0.00646 0.0133 0.0145 0.0525
0.590 0.669 0.627 1.07 0.417
0,0193 0.0180 0.0209 0.0299 0.0461
0.295 0.464 0.334 1.06 0.276
0.0573 0.0616 0.0655 0.105 0.128
5.58 3.72 5.52 7.73 4.31
0.151 0.130 0.183 0.264 0.564
104
-------
backwashing also increases when the Zimpro system and vacuum filter go on-
line, however, since these effects are not directly related to heavy metals,
no additional study was done.
The weekly pattern of effluent BOD5 was examined, anticipating a
correlation to metal loading. As Figure 33 shows, no long-term pattern
related to the weekly variation of heavy metal loading with peaks during the
week and low points on weekends. A weekly pattern seems to exist from about
days 20 to 50 when the effluent BOD? decreases on weekends. However, heavy
metals are not solely responsible since this decrease is absent from the rest
of the sampling period. These results are consistent with other findings that
the treatment process recovers very rapidly from a metal spike. Also,
Kokomo's plant has been acclimated to high metal loading for a long time, so
results are not surprising.
Figures 31 to 39 show the frequency distribution of each of the seven
heavy metal concentrations in the plant effluent. These distributions are
plotted, using a logarithmic ordinate scale, necessitated by the wide range in
measured effluent concentrations. Distribution curves indicate that they may
really result from two log-normal distributions superimposed on one another.
At higher concentrations, one log-normal distribution may account ".for plant
upsets. At lower concentrations another distribution may account for day-to-
day variability in plant effluent. These two distributions characterize plant
removal of heavy metals.
Finally, several attempts were made to correlate metal concentrations to
suspended solids. It was- hoped a linear relationship would result, for
example: --
Metal Cone. * (Const.,) (SS) +> (Const2).
If so, soluble metal could be estimated as (Const?) However, when dene at
several treatment plant points, for example, the plant influent, the primary
influent and effluent, the MLSS, the secondary and plant effluent, no
correlation was possible. Correlation coefficients for a linear least-squares
fit ranged from -0.09 to 0.06.
CONCLUSIONS
(1) The Kokomo, Indiana, activated sludge, municipal sewage treatment plant
is capable of high removals of heavy metals. Influent concentrations are
reduced 80 percent for cadmium, 98 percent for chromium, 85 percent for
copper, 29 percent for nickel, 89 percent for zinc, 98 percent for iron,
and 95 percent for lead.
(2) High and variable influent metal concentrations do not significantly
affect this acclimated treatment plant, either with regard to metal
removal efficiencies or to five-day BOD^ and suspended solids (SS)
removal efficiencies.
105
-------
(3) A mass balance for heavy metals in a treatment plant can be reasonably
accomplished. Percent recoveries (percentage of mass of influent metal
from effluent of a particular operation) are consistently between 90 and
110 percent for all mainstream operations. Recoveries around sludge-
handling operations are consistently between 80 and 120 percent. Around
the whole.plant, recoveries were measured as follows: cadmium, 142
percent; copper, 123 percent; nickel, 119 percent; and zinc, 82 percent.
Chromium recovery was only 21 percent, which was believed to be the
result of a low measured chromium concentration in the filter cake and/or
several very large influent chromium spikes. Recoveries for iron and lead
were in the same range as the other metals in unit operations, however,
there was an insufficient sampling period for a meaningful balance for
the plant as a whole.
(4) Metals are conserved within the treatment plant and ultimately
concentrate to a very high degree in the final sludge cake. The average
metal concentrations of the filter cake were on a dry weight basis 377
mg/kg for cadmium, 1,060 mg/kg for chromim, 1,970 mg/kg for copper, 533
mg/kg for nickel, 13t600 mg/kg for zinc, 71,900 mg/kg for iron, and 9^
mg/kg for lead.
106
-------
to
Q
O
CD
60
~ 45
30
15
(98.2)
(S)= Sunday
+
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s $
H
20
30
H
40
50
Days 8-6 8-13
S S S
8-2O 8-27 9-3
S S S
9-10 9-17 9-24
60
S
10-1
Figure 33. Secondary effluent BOD^,
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0.020
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o
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u
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t I
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0.1
0.5 I 2
10 20 30 40 50 60 70 80 90 95 98 99
PERCENT OF DAYS WHEN AVERAGE CADMIUM CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED VALUE
Figure 34. Effluent cadmium frequency distribution.
-------
o
vo
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O.060
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0.1 0.5 I 2 5 |0 20 30 40 50 60 70 80 90 95
PERCENT OF DAYS WHEN AVERAGE CHROMIUM CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED VALUE
J L
98 99
Figure 35. Effluent chromium frequency distribution.
-------
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0.080 -
0.060 -
O.O40
o>
O
z
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O
O
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0.020
0.010
.
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J I I I I L
J_
J L
O.I
5 I Z 5 10 30 30 40 50 60 70 80 9O 95
PERCENT OF DAYS WHEN AVERAGE COPPER CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED VALUE
98 99
Figure 36. Effluent copper frequency distribution.
-------
1.00
0.60
0,60
O.4O
o>
O.20
I
o
o
*
o
0.010
0.008
0.006
O.O04
O.OO2
1
I L
I
0.1 0.5 I 2 5 10 20 30 40 5060 70 80 90 95
PERCENT OF DAYS WHEN AVERAGE NICKEL CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED
98 99
Figure 37. Effluent nickel frequency distribution.
-------
I.OO
O.BO
O.6O
0.4 O
0.2O
r
z
O
§ 0.10
z Q08
UJ
o
O 0.06
O.O4
O.O2
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I
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I
I
O.I O. I 2 5 10 20 30 40 50 60 70 80 90 95 98 99
PERCENT OF DAYS WHEN AVERAGE ZINC CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED VALUE
Figure 38. Effluent zinc frequency distribution.
-------
1.00
Q8O
? Q60
0.40
o
u
z
o
a:
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O.IO
O.OIO
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J I L
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J L
0.1 Q5 I 2 5 10 20 30 40 50 60 70 80 90 96 98 99
PERCENT OF DAYS WHEN AVERAGE LEAD AND IRON CONCENTRATION
IS LESS THAN OR EQUAL TO INDICATED VALUE
0.004
-------
SECTION 4
SOURCES AND FLOW OF HEAVY METALS AND CYANIDE IN
THE KOKOMO, INDIANA, MUNICIPAL SEWER SYSTEM
INTRODUCTION
The objective of this study was to establish a protocol to assist
communities in identifying, quantifying, and formulating regulatory policies
for reduction of heavy metal and cyanide discharges to publicly owned
treatment works (POTW) to the point that land disposal of sludge would be
feasible. Several independent protocols had to be established or developed to
accomplish this.
Establishment of a routine to obtain the most representative samples from
likely sources (nonpoint, point, and street surface) was of primary
importance. This involved determining: (1) sampling station locations, (2)
metals and cyanide coverage, and (3) sampling frequencies. A second important
area was development of an analytical method for metal and cyanide sample
analysis. An EPA analytical procedure was modified for analysis of wastewater
samples. The final concern was establishment of pretreatmejit strategy
alternatives to reduce metal and cyanide inputs to the sewer network of a
representative city to levels consistent with land disposal of digester
sludge. The control strategy evolved during this study can be implemented by
modifying present city ordinances which limit concentrations of metals and
cyanide in industrial waste discharged to the sewer network. Guidelines and
restrictions for various industrial categories not presently regulated must be
promulgated.
Study Site Selection
The prototype community selected for this study was Kokomo, Indiana. It
is a medium-sized city (42.000) with (from the sampling and analysis point of
view) a manageably sized, combined sanitary and storm sewer treatment network
that serves well-defined residential areas and a diverse industrial community.
The industrial and commercial comlex of Kokomo includes operations such as
electroplating, metal fabricating, automotive manufacture, chemical
processing, and food processing.
Kokomo was chosen for the study for several reasons. Sewer system
networks of large cities are so complex that they virtually defy definitive
flow analysis and/or quantitative source identification. Smaller communities
tend to have atypical residential-industrial flow compositions. Kokomo
provided a wastewater flow mixture typical of an industrialized city (i.e.,
114
-------
one that has neither an over-abundance nor a paucity of domestic or industrial
sources discharging to the sewer network).
The treatment facility that serves the city of Kokomo is a newly
renovated, 30 mgd activated sludge/multimedia gravity filter plant. Because
of the contribution of substantial quantities of metals from various metal
operations within the city, this particular P07W has experienced problems, not
only with the treatment facility itself, but also with disposal of its
digester sludge. This situa-tion provided an excellent opportunity to
investigate these problems.
The Kokomo sewer system is composed of six major trunklines serving the
city and surrounding areas. Three of these trunklines are classified as
purely residential, whereas the other three carry a combination of
residential, commercial, and indus4ngal waste water. The city layout is such
that the northern section Colder part) is served by a combination storm and
sanitary collection network, with overflows going to Wildcat Creek. The
southern section of the city (new part) is served by a separate storm and
sanitary collection system. Storm water is discharged to the Wildcat and
Kokomo Creeks.
The metals originally chosen for this study were cadmium, chromium,
copper, lead, mercury, and zinc. These particular metals were chosen because
of their potential toxic effects on human health and the environment,
primarily in respect to land disposal of sludge and to discharge of treated
wastewater. Atomic absorption (AA)spectrophotometry was the method selected
for trace metal determination because of the anticipated large number of
samples and the ease and efficiency of analysis. A3 the project proceeded,
mercury was excluded from the original list because of the extended amount of
time needed for determination.
Total cyanide was also analyzed in this study, primarily because of its
known association with trace metals in wastewater discharges from
electroplating plants. The determination of total cyanide was carried out by
a distillation-scrubber collection system and a pyridine-barbituric acid
colorimetric procedure. Cyanide amenable to chlorination was also initially
considered, but it was excluded because of the large number of samples
expected and the necessity for rapid analyses. In addition, preliminary
analysis revealed no measureable quantities of cyanides amenable to
chlorination in the municipal and industrial wastewater. Only one industry
treated their cyanide-based plating wastewater.
METHODS AHD PROCEDURES
Sampling Protocol for Characterizing Metal and Cyanide Transport in Sewer
Colleccion Systems . '
Trunkline sampling was conducted from April, 1978, to June, 1979, at
twelve locations in the Kokomo sewer network_(Figure 40). These locations
were chosen to characterize metal and cyanide input to the treatment plant.
115
-------
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Automatic sequential samplers (ISCO-1680)1 and continuous flow recorders
(Stevens F-63)^ were used at each sampling location to measure metal and
cyanide mass flow rates. Metal and cyanide samples were collected at each
site in 500-ml acid-washed polyethylene bottles preserved with 2-ml 1:1 nitric
acid for total metals and 2-ml 1CN sodium hydroxide for total cyanides.
Samples were obtained^ for each trunkline at 2-hour intervals for three
2U-hour periods. Sampling was conducted on a Monday through Thursday
schedule, when feasible, to avoid any unusual fluctuations in flow or metal
and cyanide discharge due to variations in industrial work schedules or
increased residential activity during the weekend. Flow rates were determined
using a combination of continuous flow recorders and sharp-crested weirs.
Sampling Site Selection
One of the most critical steps in any sewer monitoring program is the
selection of appropriate sampling site locations. An appropriate sampling
site is one which provides: (1) easy accessibility to and from the site, (2)
sufficient space to install sampling and flow recording equipment, (3) a
suitable location with little or no slope and a straight section of the sewer
to obtain accurate sampling and flow data, and (4) a critical point in the
collection system foe quantification of flow and pollutants.
Site selection during this study was difficult. Most problems involved
insufficient space for sampling and flow recording equipment and/or sloped
sewers with no straight sections in which proper weir construction was
possible. An inordinate amount of time was spent searching for optimal
sampling site locations. Figure40 shows the final sampling sites used to
obtain flow, metal, and cyanide data for the trunkline survey.
Selection of Flow Measuring Equipment
The selection of the proper flow measuring equipment is perhaps the
second most critical step in a sewer monitoring program. To select the
appropriate type of flow device to measure a particular open channel flow,
there are several considerations: (1) sample site conditions, (2) anticipated
range of flow, (3) composition and type of waste to be measured, (4) allowable
head loss, (5) required accuracy, and (6) site preparation cost.
With this information, it was determined that sharp-crested, V-notched,
and Cipolletti weirs would be used for flow measurements. These weirs are
simple to construct and easy to maintain on a short-term basis, and provide
sufficient accuracy for flow determination. The primary disadvantages of
weirs are the potentially high head loss and susceptibility to settling and
accumulation of suspended particulates in the approach channel behind the
upstream face. These factors can lead to inaccurate flow measurements and
were regarded as negligible.
1 ISCO, Lincoln, Nebraska.
Leupold and Stevens, Inc., Beaverton, Oregon.
117
-------
The 90° V-notch weir was used to measure flows of less than 2 cfs (0.65
MGD). This weir was used primarily to monitor residential trunklines. The
formula for flow with the 90° V-notch weir is:
Q 3 2.49 H2'5
where flow, Q, is in cfs, and H is the head measured in feet.
The Cipolletti weir was used to measure larger flows, s.uch as those
encountered in the trunklines which had a mixture of residential, commercial,
and industrial wastewater. The flow formula for the Cipolletti weir is3:
Q = 3.37 LH1-5
where
Q = discharge (cfs)
L = length of the weir opening at the base (feet)
H s measured head (feet)^
Weir Construction and Installation
The manhole installation procedure for weir construction was in most
cases similar for all sampling locations. The weir construction schedule, and
therefore the time required to complete the trunkline sampling program, was
greatly extended by the unusual difficult and long winters of 1978 and 1979.
Extremely heavy snowfall and cold temperatures not only made construction and
sampling virtually impossible during much of the winter season, but also
contributed to a longer and heavier than usual spring thaw. The latter
resulted in such high flows in trunklines due to street runoff and
infiltration that weir construction and sampling were severely curtailed.
A profile of the sewer bottom was first determined by taking vertical
measurements at intermittent distances across the sewer channel. A bulkhead,
constructed out of 3/4-inch marine plywood, was then cut to fit this profile.
An accurate V-notch or Cipolletti was constructed by first cutting the desired
notch shape in the bulkhead and then mounting strips of 2-inch aluminum on the
upstream side of the weir to fit the notch. The edges of the aluminum strips
were positioned 1 inch away from the edges of the plywood to insure a knife-
edge flow over the weir. Figure 41 shows a constructed Cipolletti weir ready
for installation. The bulkhead was anchored in place by 2-by-4-inch bracing
and Ramset4 anchors. Special care was taken to insure proper horizontal and
vertical alignment. The flow around the bulkhead was sealed by using hemp
rope (okum) and putty. A porcelain-covered steel staff gauge was positioned
upstream and located so that "0" on the gauge corresponded to the elevation of
the weir crest (Figure 42).
Stevens Water Resources Data Book, 3rd ed., Beaverton, Oregon.
Ramset Fastening Systems, Branford, Connecticut.
118
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X. mounting platform was then built for the flow recorder. A Stevens Type
F level recorder was used for flow measurements. A 24-hour, mechanical clock
was used to control the strip-chart flow recorder (Figure 43), and a stilling
well was constructed, using 5-inch diameter plastic drainpipe. The well was
positioned upstream from the weir plate.
A framework of 2 x 2 inch boards was constructed for the IS-CO automatic
sequential sampler (Figure 44). The sampler strainer was positioned in the
middle section of the channel flow just upstream from the weir. Figures 45
and 46 illustrate the construction and installation of a Cipolletti weir. The
flow recorder and sequential sampler were also installed and ready for
operation.
Trunkline Monitoring Difficulties
The adverse effect on trunkline sampling of unusually severe winter
weather has been discussed. Submersion of weirs during frequent high flow
periods prevented sampling for more than 120 days, during the survey period,
and high flow conditions also resulted in destruction of several installed
weirs. Damage to one of the automatic samplers was also attributed to high
flow conditions. Attempts to construct and install weirs and conduct a
complete sampling program during the months of February, March, and April met
with extraordinary difficulties.
Analytical Techniques for Determining Metal and Cyanide _in Wastewater
Heavy Metals in Wastewater
Samples for metal analysis were collected in 500-ml acid-washed
polyethylene bottles containing 2 ml of 1:1 redistilled nitric acid. After
collection, the samples were transported to the laboratory, logged in, and
readied for sample preparation. Representative aliquots of 150 ml of
homogeneous sample were transferred to a 200-ml Berzelius beaker and 5 ml of
redistilled nitric acid was added. The samples were then placed on a hot
plate and allowed to evaporate to dryness at low heat setting (no boiling
should occur). More sample and nitric acid were added to the same beaker and
the sample evaporated again.
This was done three times, using a total of approximately 400 ml of
sample and 15 ml of redistilled nitric acid. Five ml of redistilled nitric
acid were then added to the dried sample and the sample refluxed for 1 1/2
hours by placing a watchglass on top of the beaker and heating at a low
setting. After 1 1/2 hours, 5 ml of hydrochloric acid (HCL, 37 percent) was
added and the sample refluxed for another 1 1/2 hours. At the end of the
second refluxing, the watchglass was removed and the sample allowed to
evaporate to dryness.
Five ml of redistilled nitric acid were added and the sample heated at a
low setting for a few minutes to solubilize the salt. Sample contents were
then transferred to a 10-ml volumetric flask using a Pasteur pipette. The
beaker was rinsed with double distilled water and the water used to bring the
sample to the 10-ml volume.
121
-------
'l~, **.-«.*<$»*»,, C^/3
" "c- i
Figure 43. A 24-hour mechanical clock to control the scric-cha;
flow recorder.
U4^
-------
Figure 44. An ISCO automatic sequential sampler consisting of a 2-inch by
2inch, board framework.
123'
-------
Figure 45. The construction of a Cipolietti weir,
124
-------
Figure 46. The installation of a Cipolletti weir.
125.
-------
Appropriate dilutions were made when necessary in 1:1 redistilled nitric
acid. Samples were analyzed by atomic absorption spectrophotometry (Perkin-
Elmer 5,000), using a deuterium arc background corrector. Appropriate
standards were prepared for the metals by diluting stock solutions of cadmium,
chromium, copper, lead, nickel, and zinc in 1:1 redistilled nitric acid and
analyzing them in a manner similar to the field samples.
Accuracy and Precision of Metal Analysis
The accuracy of metal analysis is mainly affected by systematic errors.
These errors are not attributed to random fluctuations in analytical
procedures. In this study, they included: (1) loss of metal during
concentration, digestion, and transfer of samples to volumetric flasks, (2)
matrix effects due to difference in viscosity of the sample solutions or to
insolubility of metal in the matrix, and (3) background absorption due to
dissolved salts.
Loss of metals during concentration, digestion, and transfer of samples
is negligible. Table 56 shows the results of analysis of 12 "unknown" metal
samples supplied by EPA to the laboratory. All samples were concentrated 25-
fold, and were digested and transferred to volumetric flasks, using the same
protocol as for sewage samples. The mean percentage recovery for these
samples was 103-3 'percent and the median 101.4 percent, indicating no
detectable loss from digestion and transfer.
Interference in metal analysis as a result of matrix effects and by
background absorption due to dissolved salts was measured by the "method of
additions." Sewage samples were concentrated, digested, and analyzed before
and after "spiking-" with "unknown" metal samples supplied by EPA. The amount
of unknown metal was calculated as the difference between the metal content of
the sewage samples before and after spiking. As shown in Table 57, the mean
percent recovery of unknown metal in the spiked samples was 96.5 percent and
the median, 95.7 percent. Interference by matrix effects and background
absorption resulted in a syteraatic understatement of metal concentrations of
approximately U percent.
A second group of errors which generally affect the precision of metal
analysis are those which introduce random fluctuations into the analytical
procedure. These errors, however, would not interfere with overall accuracy
of metal analysis. Random errors included: (1) Errors introduced by improper
homogenization of sewage samples prior to removal of measured aliquots for
digestion. In most instances, this source of error was eliminated by
analyzing the entire sewage sample collected (500 ml), (2) Errors introduced
by inaccurate standard metal solutions. These errors were considered
negligible since analysis of "unknown" metal samples supplied by EPA gave
values close to "true" ones (see Table 58). (3) Instrumental errors
introduced by short-term fluctuations in baseline absorption and longer-term
drifts in absorption. These instrumental errors were responsible for most of
the variabilility in the precision of analysis. Table 53 gives estimates of
percent standard deviations for replicate sewage samples concentrated and
digested before analysis. These estimates are for samples concentrated 40-
fold during digestion, and do not account for systematic errors or errors in
accuracy of the standards. As can be seen in Table 58, the percent standard
126
-------
TABLE 56. RECOVERY OF UNKNOWN METAL SAMPLES
SUPPLIED BY EPA1
Metal
Zinc
Zinc
Cadmium
Cadmium
Copper
Copper
Chrone
Chrome
Nickel
Nickel
Lead
Lead
nrg/1
0,17**
0.030
0.073
0.023
0.102
0.073
0.209
0.154
0.152
0.045
0.352
0.298
Percent
Recovery
97.7
124.7
94.6
100.0
100.0
100.3
95.2
103.9
102.6
108.4
102.3
110.0
Mean - 103.3
Median - 101.4
1 Samples were concentrated 25-fold prior
to analysis.
Average of three analyses.
127
-------
TABLE 57. RECOVERY OF UNKNOWN METAL SAMPLES ADDED
TO SEWAGE PRIOR TO DIGESTION AND
CONCENTRATION*
Metal
Zinc
Zinc
Cadmium
Cadmium
Copper .
Copper
Chrome
Chrome
Nickel
Nickel
Lead
Lead
Initial Metal
Cone (mg/1)
0.174
O.Q3C
0.073
0.023
0. 102
0.073
0.209
0.154
0.152
0.045
0.352
0.298
Mean percent
Median percent
Percent
Recovery
102.3
103.7
91.2
93.5
94.4
97.7
93.3
91.6
91.4
97.1
100.6
101.7
recovery - 96.5
recovery - 95.7
* Sewage samples spiked with unknowns were concen-
trated 40-fold prior to analyses. Regular sewage
samples were also concentrated 40-fold prior to
analyses. Unknown metal values were calculated
by subtracting sewage sample values from spiked
sewage sample values. Average of three samples.
128
-------
v£>
TABLE 58. ESTIMATED PERCENT STANDARD DEVIATIONS AT NINE INITIAL METAL CONCENTRATIONS
FOR REPLICATE SEWAGE SAMPLES CONCENTRATED 40-FOLD DURING DIGESTION*
Cadmium
Zinc
Chrome
Copper
Nickel
Lead
0.00025
79
114
<125
<125
<125
<125
Initial (preconcentration) Metal Concentration (mg/1)
0.00050 0.00100 0.00250 0.00500 0.01000 0.02500 0.05000
41
60
83
<125
<125
<125
22
34
42
80
<125
<125
15
18
18
32
106
<125
10
12
10
19
54
96
4.5
9.7 ' '
6.1
12
28
48
4.0
8.1
3.6
5.8
12
21
4.0
8.1
2.8
4.0
7.2
11
0.10000
4.0
8.1
2.8
3.8
4.6
6.7
Errors resulting from matrix effects, background effects, systematic loss of metals
during concentration, or Inaccurate standards would not be measured.
-------
deviations for metal analyses tends to increase sharply with decreasing
initial metal concentration. Table 59 lists the limits of detectability for
the six metals analyzed. The limit of detectability was reached when the
relative standard deviation was 50 percent.
Metal Values for Analysis of Replicate Samples
To determine the precision of metal analysis in acid-digested
concentrated sewage samples, four samples were analyzed five times and one
sample was analyzed six times. The values for each sample for each analysis
are shown in Table 60. For the sewage sample analyzed six times, the percent
difference between three groups of t~wo samples was computed and the average
entered in Table 61.' A comparison was also made of the absolute difference in
metal value between three groups of two samples. The average value of the
absolute difference was C.13 mg/1 for cadmium, 0.0 mg/1 for chromium, 1.7 mg/1
for nickel, 5 mg/1 for lead, 6 mg/1 for zinc, and 2 mg/1 for copper (Table
61).
Cyanide _in_ Wastewater
In general, the procedure used for cyanide determination was that
described in the EPA-publication, Methods for Chemical Analysis o_f Water and
Wastes, 1974. The ~500-ml cyanide samples were collected in acid-washed
polyethylene bottles to which 2 ml of 10 N NaOH and 10 ml of 3 percent
ascorbic acid in a vial had been added prior to collection. This preamendment
method was carried out to minimize the destruction of cyanide due to delayed
sample analysis (although sample analysis was performed within 21 hours in
most cases) and to minimize the effect of interfering substances, such as
oxidizing agents. Thus the NaOH maintained the samples at a pH of >J2.0,
while the ascorbic acid "destroyed most of the oxidizing agents (bleaches)
present at the time of sampling.
At the time of collection, the cyanide samples were kept cool by
arranging them in the innermost circular configuration in the center of the
sequential sampler into which ice had been placed. The ice maintained a cool
environment (4° C) not only while the sampling was being carried out, but also
while the samples were being transported back to the laboratory for analysis.
At the laboratory, each cyanide sample was logged in and tested for
sulfides and additional oxidation agents by using lead acetate and potassium
iodide-starch test papers, respectively. If these interfering compounds were
present, further treatment was carried out according to the procedures
outlined in the EPA methods.
Distillation of the samples was carried out in the following manner. A
known amount (approximately 500 ml) of sample was placed into a 1 liter
boiling flask. The boiling flask, condenser, and absorber (Milligan-Fisher
scrubber with 250 ml of 0.2 N NaOH) were then connected to the vacuum source.
A slow steady stream of air was maintained in the boiling flask by adjusting
the vacuum source so that approximately one bubble of air per second entered
the absorber through the absorber-inlet tube.
130
-------
TABLE 59. LIMIT OF.DETECTABILITY FOR HEAVY METALS
Limit of
Metal Detectability (mg/1)
Cadmium 0.0004
Zinc " 0.0006
Chrome 0.0008
Copper 0.002
Nickel 0.005
Lead 0.010
The limit of detectability was reached when the
relative standard deviation was 50 percent.
Values are for initial metal concentrations in
samples concentrated 40-fold during digestion.
TABLE 60. METAL VALUES FOR ANALYSIS OF REPLICATE SAMPLES
frmr* ___ - - «,.,..«, M**h il fmrr/1 ^ ____,.,
Sample Factor Copper Zinc Nickel Lead Cadmium
{Sewage 40. 15 0.063 0.094 0.003 0.021 0.0003
i
{Used 40.15 0.068 0.092 0.005 . 0.014 0.0004
i
t
!For 40.15 0.068 0.103 0.006 0.014 0.0003
I
{EPA 40.15 0.068 0.114 0.006 0.007 0.0001
{"Unknown" 40.15 0.068 0.089 0.007 0.017 0.0003
i
i
{Analysis 40.15 0.067 0.093 0.004 0.017 0.0004
Average 0.067 0.079 0.005 0.015 0.00028
Std Dev 0.0021 0.0094 0.0014 0.0047 0.000098
% Std Dev 3.17 9.7 28 32 35
Chrome
0.056
0.058
0.058
0.058
0.056
O.C56V
0.057
0.0011
1.9
131
-------
TABLE 61. METAL CONCENTRATIONS FROM ANALYSIS OF DUPLICATE SAMPLES
- Metal ~~~
Cadmium Chromium Nickel Lead Zinc Copper
Average percent
difference between
three groups of 2
samples for sewage 66 1 47 50 5 3
samples annalyzed
6 times
Average difference
between three groups
of 2 samples for
sewage samples 0.00013 0 0.0017 0.005 0.006 0.002
analyzed 6 times
(mg/1)
After air flow adjustment, 20 ml of concentrated sulfuric acid was slowly
added to the boiling flask through the separatory funnel. The funnel was
rinsed with distilled water and the sample and acid allowed to mix with the
air flow for 3 to 5 minutes. An additional 10 ml of 3 percent ascorbic acid
were added to the sample and the separatory funnel rinsed with distilled
water. Finally, 10 ml of cuprous chloride (Cu? Cl?) reagent were added to the
sample and the separatory funnel rinsed with distilled water again. The
contents of the flask were then heated to boiling, being careful to prevent
the contents from backing up and overflowing out of the air inlet tube. The
samples were distilled-refluxed for 1 hour. The heat was then turned off and
the air flow allowed to continue for an additional 15 to 20 minutes for cool-
down. After cool-down, the boiling flask, absorber, and vacuum source were
disconnected.
The solution in the absorber was transferred into a volumetric flask and
brought to volume with distilled water washings from the absorber inlet tube.
A 25-ml aliquot of this solution was transferred to a 50-ml volumetric flask
and the cyanide concentration determined colorimetrically. The pyridine-
barbituric colorimetric method used was similar to that outlined in the EPA
procedure, with the exception that 7.5 ml of sodium phosphate solution, 1 ml
of Chloramine T solution, and 2.5 ml of pyridine-barbituric solution were
used. Distilled water was used to bring the sample to volume. After a color-
developing time of 8 minutes, the sample absorbance was read on a
spectrophotometer (Perkin-Elmer, Coleman 44) at a 578 nm wavelength within 15
minutes. A standard cyanide curve was prepared by diluting suitable volumes
of standard solution to 500.0 ml with distilled water and plotting absorbance
of standard versus cyanide concentration.
132
-------
The percent recovery for this method is presented in Table 62. The
cyanide recovery was adequate down to 0.2 mg/1, where it decreased sharply.
TABLE 62. RECOVERY OF CYANIDE AS A FUNCTION
OF INITIAL CONCENTRATION WITH
DISTILLATION COLORIMETRIC METHOD
Concentration (mg/1)
0.50
0.40
0.30
0.20
0.10
Percent
Recovery
100.0
98.3
91*0
88.3
62.6
The precision of this procedure is presented in Table 63. The values
shown as relative standard deviation represent three samples, each analyzed
four times. The precision of the method was adequate down to 0.1 mg/1
concentration, where it also dropped off dramatically. Sensitivity of the
procedure was 0.02 mg/1.
TABLE 63. PRECISION OF THE CYANIDE DISTILLATION
COLORIMETRIC METHOD
Relative Standard
Concentration (mg/1) Deviation
0.40
0.30
0.20
0.10
7.4
9.1
21.2
20.3
133
-------
POINT SOURCE TESTING
The quantification of metal and cyanide input from specific industries to
the Kokomo sewage treatment plant yielded much information. The point source
survey of Kokomo industries provided a data base which operators of other
publicly owned treatment works (POTW) may utilize to estimate metal and
cyanide input to their particular collection systems. Where treatment was
practiced, sampling raw and treated wastes of point sources discharging to the
Kokomo system provides operators of other sewage treatment plants with
information on degrees of pollutant removal which are feasible for the types
of industries surveyed here. This information enables other POTW operators to
determine technologically feasible limits of control for industries they serve
so that a reduction in heavy metal and cyanide levels in sludge would make
land disposal a feasible alternative.
Twelve known point sources of heavy metals and cyanide identified by
Standard Industrial Classifications (SIC) were sampled in this study over a 3-
month period in 1979 (see Figure 40). Flow data from these point sources were
obtained from flow meters and/or city water meters available at each one. In
one case, a pair of V-notch weirs with a recording depth-of-flow indicator
(Stevens flow recorder and float) was employed to measure flow afaove_and below
the point of discharge.
Waste streams were sampled at two hour intervals for three consecutive 24
hour periods (days). Metal and cyanide samples were collected using an
automatic sequential sampler (ISCO). The treatment and analysis of these
samples are described elsewhere in this report. Table 64 lists the point
sources and identifies each one by a brief description of its industrial
function.
Point Source J_
Point Source 1 is a major manufacturer of automatic transmissions and
aluminum die castings for the automotive industry. Its transmission and
casting facilities are the two largest operations of their kind in the world.
Over 9,000 transmissions are produced daily and nearly 2.5 million are
manufactured annually. The Kokomo casting plant die casts some 122 different
parts, including transmission cases, extension valve bodies, and transfer
plates.
Effluent wastes from the transmission plant and die cast plant are
collected in a common receiving pit for solids settling. Overflow from the
receiving pits is transferred to one of four batch tanks (one tank is
currently being used as a oil/water separator). Underflow (solids) is
transported to an approved landfill for ultimate disposal, and each batch tank
is then treated with acid, caustic, alum, polymer coagulant aid, and polymer
emulsion breaker, depending upon treatment required. Treated effluent from
the batch tank is discharged to the Kokomo sanitation network. Solids that
settle from the batch tank processes are returned to the receiving pit for
ultimate reprocessing and disposal. Oil from the oil-water separator and
skimmings from the three other batch tanks are> sent through a series of skim
oil holding tanks for heating (140° F) and acid addition to enhance decanting.
134
-------
TABLE 64. LIST OF POINT SOURCES IN KOKOMO BY INDUSTRIAL
PRODUCT OR SERVICE
Point Source Product
1 Aluminuum die casting
Automatic transmissions
2 Electroplating
3 " Electronic semiconductor components
U- Electroplating
Metal products
5 Electroplating t
6 High and low carbon
Wire products
7 " Galvanizing
8 Aluminum products
9 Nickel-, cobalt-, and iron-based alloys
Melting, forging, hot rolling
10 Nickel-, cobalt-, and iron-based alloys
Cold rolling and fabrication
IT Laundry services
12 Printing services
Decanted water is either transferred back to the receiving pit or neutralized
with caustic (3 percent) and blended in with j;he batch treatment effluent
discharged to the city sewer system. Oil from :the holding tanks is filtered
to strip out remaining solids, and spent filter cake from the filter is
transported to a landfill for approved disposal!. Ultimate separation of oil
and water occurs in a final tank before oil reclamation. Decant from the
reclaimed oil tank is discharged to the city sewer system. The final effluent
from Point Source 1 is presented in Table 65.
Point Source _2
Point Source 2 primarily conducts circuit board plating operations and
also does some soldering and assembling of radiq components. One of the main
radio components constructed at this location is bridge audio work. The
135
-------
TABLE 65. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 1
TO NEW PETE'S RUN (T-3) TRUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
Cmgd)
0.496
0.379
0.446
0.440 '
0.059
Pounds Per Day
Cd
0.006
0.004
0.004
0.005
0.001
Cr
0.034
0.018
0.048
0.033
0.015
Ni
0.28
0.16
0.21
0.22
0.06
Pb
0.14
0.088
0.080
0. 10
0.03
Zn
3-02
1.32
1.40
1.91
0.96
Cu
0.20
0. 16
0.44
0.27
0.15
CN~
<0.42
<0.33
<0.38
<0.38
0.05
treatment facilities at Point Source 2 are primarily intended to treat
electroplating effluents.
All process waste from the circuit board plating operations goes to the
treatment facilities, where two types of waste are treated: metal-bearing
wastes (general waste) and diluted concentrations of cyanide-bearing wastes
(cyanide waste). Treatment of each is of the batch process type, in that the
waste liquid is treated, held, and monitored for quality before discharge
(Figure 47).
General waste treatment consists of pH adjustment and precipitation of
heavy metals, such as hydroxides. Chemical reactants for pH control are
sodium hydroxide to raise the pH and sulfuric acid to lower it. A pH of 9-0
is maintained in the general treatment tank to enhance settling. The general
waste treatment process includes provisions for treating cross-contamination
within the plant collection system of cyanide wastes. There are two general
waste tanks holding 0.93 million gallons each.
Cyanide waste treatment consists of two-phase destruction of cyanide to
carbon dioxide and nitrogen gases. This process adds sodium hydroxide to
raise the pH to 10.5, while adding chlorine gas in the recirculation line.
the pH is reduced to 8.5 and chlorine added until cyanide destruction is
complete. There are two cyanide waste tanks holding 0.18 million gallons
each.
After treatment, effluent from the general waste and cyanide waste tanks
is pumped into a waste blending tank (30,000 gal). Provisions are
incorporated to add either additional caustic or acid for pH trimming. The
liquids flow from the blend tank into a solids contact reactor clarifier where
a coagulant aid is added to enhance flocculation and particle agglomeration.
The overflow from the clarifier flows into the Kokomo sewer system. The
underflow from the clarifier is next pumped into two sludge thickeners, which
operate either in parallel or in series for optimum dewatering and sludge
concentration. Any overflow from the sludge thickeners is returned to the
general waste system. The thickened sludge is pumped to a sludge conditioning
136
-------
Cyanide
Wastes
Par shall
Flume
Cyanide
Treatment
Tanks
(3)
PH
9.0
OVERFLOW
UNDERFLOW
General
Waste
Treatment
Tank
3
Sludge
Condi tione
Rotary
Vacuum
Filler
FILTRATE
General
Wastes
Sewer
Outfall
Sludge Land
Disposal
Figure 47. Treatment system for Point Source 2.
-------
tank where additional mixing takes place and filter aid (prefilter chemical)
is added if necessary. The conditioned sludge flows by gravity to one of two
rotary vacuum filters for final dewatering. The filtrate liquid is returned
to the general waste system, and solids are collected for hauling to an
approved landfill for ultimate disposal. The effluent of Point Source 2 is
presented in Table 66.
TABLE 66. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 2
TO MEW PETE'S RUN (T-3) TRUNKLINS
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.720
0.270
0,324
0.438
0.216
Pounds Per Day
Cd
0. 19
0.044
0.054
0.096
0.082
Cd
0.11
0.032
0.034
0.058
0.045
Ni
C. 19
0.034
0.034
0.086
0.090
Pb
-------
Co
IO
Fluoride
Treat-
ment
Tanks
(4)
UNDERFLOW
Treated Fluoride
pH 7.O-8.O
Cyanide
Treatment
Tanks
(3)
UNDERFLOW
General
Waste
Treatment
Tank
(3)
General
Wastes
Rotary
Vacuum
Fitter
(2)
CO
Sewer
Outfa II
Land
Disposal
-------
and chlorine is added until cyanide destruction is complete. There are three
cyanide waste treatment tanks, each holding 0.19 million gallons.
Fluoride treatment consists of pH adjustment, using lime for acid
neutralization and precipitation of calcium fluoride. There are four fluoride
treatment tanks, each having a volume capacity of 7,000 gallons. Each tank is
equipped with decant valves to drain off the clear treated liquid. The clear
decant is transferred to the cyanide treatment tanks for further treatment.
The densified underflow (calcium fluoride sludge) is pumped to the sludge
conditioning tank for preparation for filtering. The calcium fluoride is
settled by gravity within 24 hours, or the settling can be improved by
addition of polyelectrolyte polymers.
Nickel treatment consists of pH adjustment for precipitation of nickel
hydroxide. A backup system of nickel treatment consists of addition of sodium
polysulfide with precipitation of nickel sulfide. The treated nickel is
either transferred to the sludge conditioning tank, or transferred to the
other fluoride treatment tanks to blend with calcium fluoride sludge. There
are two 750 gallon storage tanks for nickel wastes. Nickel treatment is
performed in the fluoride treatment tanks after being transferred from the
storage tanks. At the present time, however, nickel operations are.inactive.
Chromium treatment is a self-contained batch process remotely located
from the treatment facility. The process consists of collecting the small
volume of plating rinse water in a treatment pit. Sulfuric acid and sulfur
dioxide are added to maintain a pH below 3.0 while providing an electron donor
material: sulfur at plus four valence. Chromium is continuously reduced from
the hexavalent to the trivalent form. Circulating pumps recirculate the
treatment liquid back to the rinse tank.
After treatment, liquid from the general waste, cyanide waste, and
fluoride and nickel tanks is transferred to a waste blending tank into a
contact reaction well clarifier, where coagulant is added to enhance
flocculation and particle agglomeration. The overflow goes from the clarifier
to the Kokomo sewer system. The underflow from the clarifier is pumped into
two sludge thickeners which can operate either in parallel or in series for
optimum dewatering and sludge concentration. Any overflow from the sludge
thickeners is returned to the system for further treatment. The thickened
sludge is pumped into a sludge conditioning tank (1,500 gallons) where further
mixing occurs, and filter aid or other suitable prefilter chemicals are added
if necessary. The calcium fluoride and nickel hydroxide sludges are combined
with other sludges in the tank, and the conditioned sludge flows by gravity to
one of two 250-square-foot rotary vacuum filters for final dewatering. The
filtrate liquid is returned to the process for further treatment, and solids
are collected for hauling to an approved landfill for ultimate disposal. The
final effluent from Point Source 3 is presented in Table 67.
Point Source £
Point Source 4 manufactures major products for the automotive,
construction, and agricultural industries. The company's products include
hydraulic piston rods for farm and commercial applications, hydraulic valves
140
-------
TABLE 67. DAILY DISCHARGE OF METAL AND CYANIDE FROM POINT SOURCE 3
TO NEW PETE'S HUN (T-3) THUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Ef f 1 uent
(mgd)
1.549
1.539
1.944
1.677
0.231
Pounds Per
Cd
0.71
0.65
0.75
0.70
0.05
Cr
0.13.
0.12
0.15
0.13
0.02
Ni
0.59
0.65
. 1.01
0.75
0.23
Pb
<0.13
<0.13
<0.47
<0.28
0.20
Day
Zn
17.98
44. 12
30.60
30.90
13. 11
Cu
3-49
5.01
5.04
4.51
0.89
CN
<1.33
2.19
£4.46
<3-55
1.67
and cylinders for agricultural and construction equipment industries, stamped
metal assemblies for air-ride sytems for trucking industries, and recreational
vehicles. Noncyanide zinc and hard chrome plating are also done at the plant.
Treatment facilities include a 600-gallon chromium reduction tank
equipped with pH controls, sulfuric acid, and sodium bisulfite feed equipment
and mixer, two 9,000-gallon batch neutralization tanks equipped with pH
controls, two mixers and caustic feed equipment, and a 50-gallon per minute
continuous belt vacuum filtration unit (Figure 49). The anticipated effluent
characteristics for both total chromium and zinc are <1.0 mg/1. These values
represent a metal removal efficiency of >99 percent for total chromium and >98
percent for zinc. Point Source 4 discharge to the Kokomo sanitary sewage
system is presented in Table 68.. At the time of sampling, the chromium
pretreatment unit was constructed but not in operation.
Point Source _5
Point Source 5 specializes in plating various manufactured products. It
provides services for both rack and barrel plating and finishes, ranging from
cadmium, hard chromium, zinc, copper, nickel, silver, and tin plating. Point
Source 5 plating operations include copper bath (150 gal); zinc bath (2,100
gal); nickel bath (4,400 gal); chromium bath (3,100 gal); cadmium bath (1,100
gal); silver bath (200 gal); alkaline tin bath (350 gal); and an acid tin bath
(150 gal). The copper, zinc, cadmium, and silver are also cyanide operations.
No treatment of metal and cyanide wastewater is presently practiced.
Effluents from plating operations are discharged directly to the Kokomo sewer
network, and acid and alkali baths are dumped to the plant waste stream once
every two weeks. The effluent from Point Source 5 is presented in Table 69.
Point Source _6_
Point Source 6 is a manufacturer of high and low carbon steel wire for
industrial and commercial use. Its products also include nails, various wire
141
-------
Chromium
Woate
Chromium
Reduction
Tank
Neutrali-
zation
Tank
(2)
VacuunA Effluent
Filtration!
pH 6-90
_^
X Sludg*
Land Disposal
Sewer
Outfall
Figure 49. Treatment system for Point Source 4.
-------
TABLE 68. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 4
TO WASHINGTON FEEDER (T-Ua-2) AND SUBSEQUENTLY TO THE
NORTH NORTHSIDE INTERCEPTOR (T-4a)»
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
- 0.095
0.092
0.093
0.092
0.015
Pounds Per Day
Cd
-------
IQ
C
fO
tn
o
-i
n>
Ol
£
n>
rt-
to
O
C
o
CD
cn
Recirculote
Cooling,
Non-Chemical
Process
Fitter Plant
6 12' dia. Units
Filter Backwash
Mill Intake
Lime
pH Control
Final
Treatment
Lagoon
Chemical
Processes
Acids Lime
and
Chemical Wastes
Reaction Tank
[AIL]
Reaction Tankr*~
Reaction Tank
T
Clarifier
-------
reclamation lagoon. Effluent from this lagoon is then transferred to a
terminal lagoon.
Chemical treatment consists of an acid neutralization facility to treat
(1) all concentrated chemical and acid wastes emanating from the mill, (2)
selected chemical and acid rinses, and (3) backlogged wastes stored in the
lagoon system. The basic facility consists of a lime neutralization process,
two 110-foot diameter clarifier/thickeners, and two vacuum filters for solids
removal. Overflow from the clarifier/thickeners is pumped directly to the
terminal lagoon, while underflow from the clarifier/thickeners is transferred
to vacuum filters. The resultant filter cake from the vacuum filters is
transported to a suitable landfill for ultimate disposal. The final effluent
from Point Source 6 is presented in Table 70.
Point Source T_
Point Source 7 conducts metal-finishing operations. The major product
from this industry is the "hot dipped" galvanizing of woven chainlink fencing.
No special treatment facilities exist at this location except the batch type
neutralization of etching acid. Discharge wastewater consists of rinse from
the alkaline process, quench water from the chainlink fencing process, and
acid drippings from the etching process. Final effluent from Point Source 7
is presented in Table 71.
Point Source 8_
Point Source 8 manufactures architectural aluminum entrances for all
types of commercial buildings. It also manufactures extruded aluminum
storefront and curtain wall systems for the commercial construction market.
The prime functions of this plant include aluminum extrusion, anodizing, and
fabrication.
Wastewater discharged to the Kokomo sewage network consists of de-ionizer
regenerant solution, water softener backwash, boiler blowdown, and anodizing
rinse waters. The nature of these wastewater constituent flows causes the
resultant effluent pH to fluctuate markedly during the course of an
operational day. As a result, Point Source 8 has a two-stage neutralization
and equalization treatment facility. Wastewater from the de-ionizers and ion
exchange regenerators is consolidated prior to discharge into an equalization
tank (10,000 gal). Sulfuric acid anodizing solution is then pumped into the
equalization tank. Anodizing rinse water and effluent from the equalization
tank are discharged into a primary neutralization tank (17,900 gal) and then
into a secondary neutralization tank (4,700 gal). Chemical feed for both
neutralization tanks consists of sodium hydroxide and sulfuric acid. Effluent
from the secondary neutralization is pumped directly into the Kokomo sanitary
sewer. The water softener backwash and the boiler blowdown are not treated.
The final effluent of Point Source 8 is presented in Table 72.
Point Source 9.
Point Source 9 manufactures high peformance nickel-base, cobalt-base, and
iron-base alloys in various forms and forgings. The company^ also produces
145
-------
TABLE 70. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 6 TO
PETE'S HUN INTERCEPTOR (T-5a)
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.381
0.384
0.384
0.384
0.0002
Pounds Per Day
Cd
0.010
<0.004
£0.008
<0.007
0.003
Cr
0. 14
0.022
0.055
0.072
0.061
Ni
0.41
0. 19
0.27
0.29
0.11
Pb
0.97
0. 16
0.27
0,47
00.44
Zn
1104.90
210.40
239.52
518.27
508.24
Cu
0.45
0.21
0.51
0.39
0.16
CN*
<0.76
<0.32
<0.33
<0.47
0.25
TABLE 71. DAILY DISCHARGES OF METAL AND CYANIDE FHOM POINT SOURCE 7 TO
THE WASHINGTON FEEDER LINE (T-4a-2) AND THE NORTH MORTHSIDE
INTERCEPTOR (T-4a) TRUNKLINE
-
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.072
0.072
0.072
0.072
0.000
Pounds Per Day
Cd
<0.001
<0.001
<0.001
<0.001
0.000
Cr
1.31
0.045
0.082
0.48
0.72
i Ni
1.12
0.26
0.33
0.57
0.48
Pb
0.039
0.045
0.026
0.037
0.010
Zn
13.53
56.49
43.56
37.86
22.04
Cu
2.43
1.46
0.49
1.46
0.97
CN~
<0.060
<0.060
<0.060
<0.060
0.000
TABLE 72. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 8 TO
THE UNION FEEDER LINE (T-45-1) AND THE SOUTH NORTHSIDE
INTERCEPTOR (T-4b) TRUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.264
0.266
0.288
0.273
0.013
Pounds Per Day
Cd
<0.001
<0.001
<0.001
<0.001
0.000
Cr
0.063
0.031
0.022
0.039
0.022
Ni
0.095
<0.088
£0.028
<0.070
0.037
Pb
0.070
0.030
0.027
0.042
0.024
Zn
0.14
2.28
1.82
1.41
1. 12
Cu
0.55
0.30
0.30
0.38
0.14
CN
<0.22
<0.22
-------
alloys as centrifugal sand, resinshell mold, and investment castings, as well
as in the form of hard facing rods, wires, and electrodes. These materials
are widely used in the aerospace, gas turbine, and nuclear industries where
high temperature and corrosion resistant metals are used.
Waste treatment facilities consist of a chromium reduction and
clarification system (see Figure 51). Two concrete equalization tanks
(131tOOQ gal each) collect wastewater from various metal operations. This
waste is then treated in a 400-gal acid mix tank with sulfuric acid and sulfur
dioxide gas. Effluent from the mix tank is pumped into a 400-gal lime slurry
reactor tank where hydrated lime is added. Discharge from the slurry tank is
then emptied into a 3tOOO-gal flocculator. This waste is pumped into a
108,000-gal reactor-type clarifier. The sludge is thickened, using a 30,000-
gal sludge thickener. Supernatant from the sludge thickener is pumped back to
the equalization tank. Sludge is hauled to the company's drying beds and
eventually transported to an approved state landfill. Other wastes from the
facility discharged to the sanitary sewer are process water, cooling tower
blowdown, boilerdown, water softener backwash, and sanitary wastes. Effluent
of Point Source 9 is presented in Table 73-
The removal efficiency of the Point Source 9 treatment system was
monitored for chromium, nickel, copper, and zinc. Sampling locations for raw
and treated metal wastes are presented in Figure 51. Metal samples were
collected every two hours for 24 hours over a consecutive three-day period.
Location 1 is where raw wastewater prior to treatment was collected. Location
2 is where wastewater after treatment was collected. Removal efficiencies for
chromium, nickel, copper, and zinc are presented in Table 74.
Point Source J_p_
Point Source 10 conducts cold^ rolling and metal fabrication operations of
various nickel-base, cobalt-base, and iron-base alloys. Machining of the
rolled and fabricated products is also carried out at this location. There
are no pretreatment facilities. The final effluent from Point Source 10 is
presented in Table 75.
Point Source JJ_
Point Source 11 provides laundry service for Kokomo residents, but no
dry-cleaning operations are conducted. Approximately 9,000 pounds of laundry
are serviced here a day. Other than normal laundering of domestic articles,
Point Source 11 also handles uniforms from various commercial and industrial
operations. No treatment facilities exist at Point Source 11. All wastewater
is directly discharged to the sewer collection network. Plant effluent is
presented in Table 76.
Point Source J_2
Point Source 12 specializes in printing magazines (12 to 13 million each
month), catalogs, brochures, books, and newspaper supplements. Water-base and
solvent-base inks are both used, depending on the application. The rolls used
in the printing process are both acid-etched and subsequently copper-chrome
147
-------
Chromium
Waste
00
Landfi II
Disposal
MeleringA Effluent Sewer
Flume } «««=£:>- Outfall
pH 7.2
Figure 51. Treatment system for Point Source 9.
-------
TABLE 73. DAILY DISCHAHGES OF METAL AND CYANIDE FROM POINT SOURCE 9 TO
OLD PARK ROAD FEEDER LIINE (T-5b) AND PETE'S RUN (T-5a)
TRUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.335
0.335
0.335
0.335
0.000
Pounds Per Day
Cd
<0.003
<0.003
-------
TABLE 75. DAILY DISCHARGES OF METALS AND CYANNIDE FROM POINT
SOURCE 10 TO OLD PARK ROAD FEEDER LINE (T-5b) AND
PETE'S SUN (T-5a) TRUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
_
0.058
0.058
0.058
0.000
Pounds Per Day
Cd
_
-------
TABLE 77. DAILY DISCHARGES OF METAL AND CYANIDE FROM POINT SOURCE 12 TO
THE SOUTH NORTHSIDE INTERCEPTOR (T-4b) TRUNKLINE
Day 1
Day 2
Day 3
Mean
S.D.
Effluent
(mgd)
0.144
0.204
0.205
0.184
0.035
Pounds Per Day
Cd
<0.002
<0.002
<0.002
' <0.002
0.000
Cr
1.95
7.29
5.38
4.87
2.71
Mi
<0.012
<0.017
<0.018
<0.016
0.003
Pb
0.041
0.084
0.085
0.070
0.025
Zn
0.069
0.083
0.065
0.072
0.009
Cu
2.91
12.32
19.20
11.48
8.18
CN~
<0.12
<0. 17
<0.18
<0. 16
0.03
Street surface accumulations were sampled to estimate the input from
street runoff of metals to the combined sanitary-storm collection system to
the Kokomo POTW. The northern section of the eity (above Wildcat Creek) was
divided into a grid composed of seven segments (Figure 52), each containing
three randomly selected sampling sites.
Collection of street surface accumulation was in June, 1979, and
conducted according to a modified method adapted from Shaheen (1975). Each
sampling site comprised an area 10 ft (3.0 m) in length parallel to the curb
and 4 ft (1.2 m) in width perpendicular to the curb. One sample was taken
from each. site. The sampling sites selected represented residential and
commercial land uses.
Both hand-sweeping and vacuum-sweeping were employed as sampling
techniques to collect surface accumulations. Each collected dry sample was
passed through a U.S. No. 12 sieve (1.68 mm). A 5.0 g subsample of the
portion of the sample passing through the sieve was placed in a Kjelkahl flask
with 20 ml redistilled nitric acid and wet digested for six hours on a heating
rack. The sample was allowed to cool and then filtered through a Whatman
fiber filter into a 10-ml volumetric flask. The filter was washed with 1:1
redistilled nitric acid and double distilled water and the volume adjusted to
10 ml. The samples were analyzed for zinc, copper, lead, cadmium, nickel, and
chromium by AA. Each street dust sample was run in triplicate. Appropriate
standards made from stock solutions and blanks were analyzed in a manner
similar to field samples.
Analysis of street surface accumulations is presented in Tables 78 and
79. Table 78 contains concentrations of heavy metals in street accumulation
found in the seven segments. The highest metal concentrations were found to
be zinc and lead. These results were not suprising when considering that the
major sources of zinc and lead are asphalt-concrete paving and leaded fuels,
respectively. The type of use (i.e., residential or commercial) was also
included for each sampling site. The results show no correlation between
151
-------
ro
IQ
cn
ro
fu
~o
o
fO
fD
ut
c:
-i.
01
o
fl)
t/l
Cu
3
-o
O
n
fu
-------
TABLE 78. CONCENTRATION OF HEAVY METALS IN KOKOMO STREET DUST (MEAN
AND STANDARD DEVIATION, ug/g)
Segment
Seg 1
a
b
c
Mean
S.D.
Seg 2
a
b
c
Mean
S.D.
Seg 3
a
b
c
Mean
S.D.
Seg 4
a
b
c
Mean
S.D.
Seg 5
a
fa
c
Mean
S.D.
Seg 6
a
b
c
Mean
S.D.
Concentration (ug/g)
Cd
1.49
0.36
1.62
1.16
0.69
0.41
2.72
0.70
1.28
1.26
1.64
3.88
0.60
2.04
1.68
0.97
2.90
1.93
1.93
0.97
2.02
3.85
2.48
2.78
0.95
0.56
1.09
2.75
1.47
1.14
Cr
7.41
0.61
3.32
3.78
3.42
0.63
3.52
1.46
1.89
1.46
1.13
1.40
2.17
1.57
0.54
1.05
4.07
4.26
3.13
1.80
1.39
3.12
4.17
2.89
1.40
1.06
1.56
3.01
1.88
1.01
Ni
30.45
40.61
36.77
35.94
5.13
10.58
43.50
22.31
25.46
16.69
21.46
18.28
33.00
24.25
7.75
23.52
83.89
84.68
64.03
35.08
56.08
61.87
54.35
57.43
3.94
20.89
37.46
65.11
41.15
22.34
Pb
1033.95
214.84
791.63
680.14
420.78
258.62
612.16
592.12
487.63
198.58
341.02
370.86
1089.10
600.33
423.55
491.12
1912.22
835.13
1079.49
741.39
520.23
712.17
1565.67
932.69
556.51
295.66
1400.76
1488.69
1061.70
664.87
Zn
312.4
100.8
357.3
256.8
136.9
125.0
543.2
225.2
297.8
218.3
130.1
117.9
263.1
170.4
80.5
220.5
2969.0
573.5
1254.3
1495.4
488.3
1051.5
523.6
687.8
315.5
156.6
305.6
558.2
340.1
203.0
Cu
91.84
10.91
302.93
135.23
150.77
16.12
195.35
46.61
86.03
95.90
24.71
42.50
53.46
40.22
14.51
18.93
231.25
274.59
174.92
136.82
50.92
178.35
63.38
97.55
70.25
32.48
60.22
110.02
67.57
39.29
Type
C*
R**
C
R
R
C/R
.
"
R
R
R
R
C/R
R
R
C
C
R
R
R
L53
-------
TABLE 78., Continued
Segment ' Concentration (ug/g)
Cd Cr Ni Pb Zn Cu Type
Seg 7
a
b
c
Mean
S.D.
Mean
S.D.
0.98
3.62
0.99
1.86
1.52
1.89
3.22
8.96
4.50
1.57
5.01
3.72
2.38
5.85
39.77
74.03
38.04-
50.61
20.30
42.70
50.22
995.04
519.53
989.30
834.62
272.89
810.91
1331.08
251.7
880.7
345.3
492.6
339.4
499.97
1601.57
19.57
34.96
61.84
38.79
21.39
91.47
240.41
R
R
R
*
C » Commercial
**
R - Residential
154
-------
TABLE 79. LOADINGS OF HEAVY METALS IN STREET DUST (LBS AND LBS/
CURB-MILE)
Segment
Pounds Metal Per Segment
Seg 1
Seg 2
Seg 3
Seg 4
Seg 5
Seg 6
Seg 7
Total
Segment
Seg 1
Seg 2
Seg 3
Seg 4
Seg 5
Seg 6
Seg 7
Cd
0.058
0.078
0.057
0.046
0.209
0.102
0.139
0.689
Cd
'0.003
0.003
0.003
0.001
0.007
0.005
0.003
Cr
2.07
1.11
0.50
0.73
1.75
0.64
8.70
15.52
Pounds
Cr
0.12
0.06
0.02
0.02
0.06
0.03
0.18
Ni
1.04
0.62
0.80
1.52
3.52
1.36
3.73
12.59
Per Curb
Ni
0.06
0.03
0.04
0.05
0.13
0.06
0.08
Pb
30.0
26.6
29.8
22.7
37.0
29.3
59.1
234.5
Mile Per
Pb
1.67
1.10
1.38
0.71
1.31
1.37
1.19
Zn
9.5
17.6
56.0
22.0
54.7
11.1
35.2
206.1
Segment
Zn
0.53
0.73
2.60
0.69
1.94
0.52
0.71
Cu
3.19
5.22
0.77
3.90
9.31
2.22
2.18
"-26.79
Cu
0.18
0.22
0.04
0.12
0.19
0.10
0.04
Total
0.004
0.08
0.06
1.20
1.06
0.14
155
-------
metal concentration and land usage. Tabla 79 gives loadings of heavy metals
from the seven segments. The highest metal loadings were found to be zinc and
lead, and again this was expected due to the sources of these two metals.
The metal loadings given are intended to serve only as a potential
"reservoir" source of metal since they would not be introduced into the sewer
collection system unless a substantial rainstorm or snow melt occurred. In
addition, in this study the combined storm-sanitation networks did not permit
an accurate determination of the quantities of metals that can wash off the
street surface and be transported to the POTW since a large fraction of the
surface runoff overflowed to the Kokomo Creek.
COLLECTION SYSTEM MONITORING
Figure 40 is a simplified version of the Kokomo sewer system indicating
trunkline sampling points and point sources. Note that there are three
primary trunklines with no known point sources discharging to them: T-1, T-2,
and T-6. Note also that T-4a receives discharges from two plating shops by
way of feeder line T-4a-2.
Analyses of was'tewater samples obtained at 2-hour intervals" in major
trunk and feeder lines are given in Appendix E. Table 80 gives waste flow and
metal flow summaries for the three major trunklines feeding the treatment
plant which have no identified point sources discharging metals or cyanide to
them (T-1, 2, 6). This study refers to these trunklines as "residential" in
nature. Conversely, Table 81 summarizes metal and cyanide flows in trunklines
receiving discharges from identified point sources (T-3, Ua, 4b, 5a), and they
are designated as "nonresidential" in this analysis. Table 82 gives fractions
of total metal input to the POTW which originate with residential and
nonresident!al trunklines.
Three North Northside Interceptor (Figure 40) feeder lines were sampled
for a 3-day period to further elucidate the relative metal and cyanide inputs
of a "residential" line (Indiana), a line receiving discharges from two
electroplating shops (Washington), and a line receiving discharge from a
commercial facility (Appersonway). Results of the sampling program are given
in Table 83. Note that Zn flow in the Appersonway feeder is extremely high
for Day 3. A check of laboratory worksheets has failed to uncover analytical
errors which would explain the elevated Zn flow. Trunkline samples collected
at 2-hour intervals between 6:00 p.m. and 4:00 a.m. exhibit an average Zn
concentration of almost 34 mg/1. Assuming the high concentrations are real,
the data strongly suggest the possibility that concentrated waste is being
dumped into the Apperson Feeder.
Table 84 suggests that the Appersonway, Washington Street, and Indiana
Street feeder lines account on the average for approximately 58 percent of the
flow in the North Northside Interceptor, and from 51 percent to over 300
percent of the flow of metals and cyanide. The fact that feeder line and
trunkline sampling was not done simultaneously evidently accounts for the HOC
percent entries on Table 84. The aforementioned anomalous high Zn flow on Day
3 of the Appersonway sampling period, together with high Zn flows in the
156
-------
TABLE 80. RESIDENTIAL INPUTS OF METAL AND CYANIDE TO KOKOMO POTW
Sampling
Day
Dixon Road
1
2
3
Mean
S.D.
Trunkline
Flow (mgd)
(T-1)
0.
0.
0.
0.
0.
380
478
406
421
051
Pounds Per Day
p
V
<0.
<0.
<0.
<0.
<0.
d
001
001
001
001
001
0.
0.
0.
0.
0.
Or
022
008
014
015
007
Mi
0.021
0.004
0.029
0.018
0.013
Pb
0.052
0.016
0.023
0.030
0.019
Zn
C.30
0.16
0.16
0.21
0.08
Cu
0.14
0.11
0.14
0.13
0.02
CN-
0.015
0.011
0.015
0.013
0.002
Fayable (T-2)
1 0.273 <0.001 0.016 0.015 0.01 0.40 0.31 0.029
2 0.661 0.001, 0.082 0.053 0.15 0.44 1.11 0.031
3 0.731 0.027 0.28 0.15 0.37 17-37 1.94 1.26
4 0.867 0.007 0.15 0.072 0.18 3-3^ 1.18 0.083
Mean 0.633 0-011 0.13 0.073 0.18 5.39 1.14 0.35
S.D. 0.255 0.011 0.11 0.057 0.15 8.11 0.67 0.61
Northwest Interceptor (T-6)
1
2
3
Mean
S.D.
Sum of
Daily Means
0.
0.
0.
0.
0.
1.
148
086
061
098
045
152
0.
0.
<0.
0.
0.
0.
001
003
001
002
001
013
0.002
0.001
<0.001
0.001
0.001
0.146
0.004
0.002
0.002
0.003
0.001
0.094
0.
0.
0.
0.
0.
0.
012
005
003
007
005
213
0.095
0.041
0.018
0.051
0.040
5.65
0.079
0.006
0.018
0.034
0.039
1.30
0.007
0.006
0.003
0.005
0.002
0.368
157
-------
TABLE 81. NONRESIDENTIAL INPUTS OF METAL AND CYANIDE TO KOKOMO POTW
Sampling
Day
Trunkline
Flow (mgd)
Morth Northside Interceptor
1
2
3
Mean
S.D.
3.76
6.-18
3.99
4.64
1.92
South Northside Interceptor
1
2
3
Mean
S.D.
Pete's Run
1
2
3
Mean
S.D.
New Pete's
1
2
3
Mean
S.D.
Sum of
Daily Means
0.854
0.903
0.829
0.862
0.053
Pounds Per Day
Cd
(T-4a)
5.0
5.2
2.2
4.3
2.3
(T-4b!
0,006
0.001
0.011
0.006
0.003
Cr
33.0
51.0
30.0
40.0
11.0
)
0.416
0.165
0.14
0.240
0.125
Ni
5.5
5.5
3-6
5.1
0.92
0.058
0.087
0.045
0.063
0.018
Pb
0.65
4.6
0.71
2.4
1.9
0.120
0.069
0.086
0.092
0.021
Zn
57.
77.
45.
62.
13.
2.
11.
2.
4.
5.
Gu
0
0
C
0
0
27
90
37
52
51
3.
6.
2.
4.
2.
1.
1.
0.
1.
0.
1
9
5
6
0
61
02
61"
08
410
CN-
1.
2.
1.
2.
0.
0.
0.
0.
0.
0.
5
9
4
1
71
089
013
024
042
034
Interceptor (T-5a)
1.53
0.961
1.33
1.27
0.23
Run Interceptor
3.057
2.628
2.286
2.657
0.386
9.43
0.067
0.044
0.018
0.043
0.02
(T-3)
3.62
3.12
2.62
3.12
0.50
7.^7
0.24
0.23
0.18
0.22
0.03
0.22
0.99
2.52
1.24
1.17
41.7
0.85
0.45
0.95
0.75
0.22
3.99
3.07
2.52
3.56
0.46
9.47
0.54
0.56
0.80
0.63
0.12
0.33
0.30
0.26
0.30
0.04
3.4
6.
5.
2.
86
4
6
4.95
1.8
14.47
8.96
6.38
9.94
4,
81
.13
.4
2.
1.
2.
98
7
9
2.5
0.59
15.82
9.
. 11
9.06
11.33
3.89
19
.5
0.4
0.
0.
0,
0.
9
5
3
5
2
8
.1
.07
.19
.15
.07
.09
.35
.84
.93
.17
158
-------
TABLE 82. PERCENT INPUT OF METALS AND CYANIDE TO KOKOMO POTW
FROM RESIDENTIAL AND NONRESIDENTIAL TRUNKLINES
Percent Input to POTW
Source ' Cd Cr Ni Pb Zn Cu CN-
Residential 0.2 0.3 1.0 5.9 6.5 6.2 4.3
Nonresidential 99.8 99-7 99.0 94.1 93-5 93-8 95.7
TABLE 83- DAILY AVERAGE METAL AND CYANIDE FLOWS IN THREE NORTH NCRTHSIDE
INTERCEPTOR FEEDER LINES
Sampling
Day
Appersonway
1
2
3
Mean
S.D.
Washington
1
2
3
Mean
S.D.
Trunkline
Flow
Feeder
0
0
0
0
0
Street
1
1
1
1
0
(mgd)
Line
.864
.852
.803
.840
.032
Feeder
.553
.575
.648
.592
.050
Cd
0.018
0.036
0.029
0.028
0.009
2.25
1.54
2.68
2.16
0.58
Cr
0.042
0.70
0.15
0.30
0.35
35.89
38.85
28.22
34.32
5.49
Pounds
Ni
0.78
0.50
0.65
0.64
0.14
1.83
2.61
4.32
2.92
1.27
Pb
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
Per Day
097
095
083
092
008
21
19
33
24
08
Zn
2.45
2.67
110.09
38.40
62.08
87.91
30.74
38.66
52.44
30.97
Cu
0.
0.
0.
0.
0.
3.
2.
13.
6.
5.
27
42
23
31
10
23
64
05
31
85
CN-
0.043
0.034
<0.001
0.025
0.023
2.26
1.08
16.13
6.49
8.37
Indiana Street Feeder Line
1
2
3
Mean
S.D.
Sum of
Daily Means
0
0
.208
.220
0.314
0
0
2
.247
.058
.68
0.006
0.001
0.001
0.008
0.003
2.19
0.091
0.005
0.13
0.075
0.064
34.7
0.007
0.007
0.088
0.034
0.047
3.59
0.
0.
0.0
0.
0.
0.
005
025
45
025
020
357
5.37
0.40
3.38
3-05
2.50
93.9
0.
0.
18.5
6.
10.
12.
070
081
3
23
65
9
<0.001
0.010
0.010
0.006
0.006
6.52
159
-------
TABLE 84. FRACTIONS OF WASTEWATER, METALS AND CYANIDE FLOWS IN
NORTH NORTHSIDE INTERCEPTOR ATTRIBUTABLE TO
APPERSONWAY, WASHINGTON STREET, AND INDIANA STREET
FEEDERS*
Total FlowPounds Per Day
(mgd) Cd Cr Ni Pb In Cu CN'
0.58 0.51 0.87 0.70 0.15 1.51 2.8 3.1
* Estimates based on nonsiznultaneous sampling of trunk and
feeder lines.
Washington feeder line which serves two electroplating shops, constitute 92
percent of the combined feeder line Zn flow to the North Northside
Interceptor. It can be seen from Tables 68 and 69 that the sum of the Zn
discharges from the;two electroplating facilities is 221.3 Ibs/day for the
respective sampling periods. This is in close agreement with the Zn flow
found in the Washington feeder line during the sampling period.
A mechanism other than comparison of overall mean flow rates can be used
to estimate whether or not measured sources of metals and cyanide account for
flows observed in a receiving trunkline. This method involves constructing
all possible combinations of daily average flows from measured sources for the
purpose of determining likely pollutant flow limits in a receiving trunkline.
For example, assume there are three sources feeding a trunkline whose
discharges have been measured (nonsimultaneously) for three days each. There
are then nine possible combinations of daily averages that may be constructed.
If it is assumed that discharges from the three sources are not correlated
(i.e. there are no process variables or maintenance practices keyed to
particular days of the week, etc.), the upper and lower flow limits resulting
from the nine possible daily average discharge combinations may be interpreted
as measures of the flow limits likely to be seen in a receiving trunkline.
This approach is referred to here as the method of "random superposition."
Its application to the three feeder lines to the North Northside Interceptor
is given in Table 85. Note that while the mean Ni flow from the three feeders
represents only 70 percent of the mean interceptor flow, the random
superposition upper limit feeder flow is 94 percent of the interceptor upper
limit. This suggests that the three feeders may account for enough of the
interceptor Ni flow that supplementary sampling would not be required to
indentify Ni point sources upstream from the feeder-interceptor junctions.
A comparison of Tables 68, 69, 71, and 83 indicates that the sum of the
mean daily Cu and CN discharges from the three point sources tested accounts
for only 40 and 25 percent, respectively, of the Cu and CN flows in the
Washington Street feeder line. This suggests the possibility of unidentified
sources of Cu and CN. However, Table 83 indicates that for two of the three
sampling days, the mean Cu and CN flows are, respectively, 2.9 and 1.7
160
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TABLE 85. RANDOM SUPERPOSITION FLOW LIMITS FOR METALS AND CYANIDE
IN COMBINED APPERSONWAY, WASHINGTON STREET, AND INDIANA
STREET FEEDERS
Flow limits (Ibs/day) """
Combined FeedersNorth Northside Int.
Parameter Upper Lower Upper Lower
Cd
Cr
Mi
Pb
Zn
Cu
CN-
2.72
39.7
5.19
0.47
203-0
32.0
16.2
1.56
28.3
2.34
0.28
33.6
2.94
1.08
5.2
51.0
5.5
4.6
77.0
6.9
2.9
2.2
30.0
3.6
0.65
45.0
2.5
1.4
pounds/day. This compares in magnitude to the sum of the Cu and CN-discharges
from Point Sources 4 and 5. The bulk of the mean Cu and CN flows in the
Washington feeder derive from high flows on Day 3. Since the other metals do
not exhibit marked relative increases for Day 3, this suggests the discarding
of concentrated Cu-CN plating waste, probably from Point Source 5, was an
alternative explanation to unidentified sources discharging to the Washington
feeder.
Point Sources 1, 2,. and 3 discharge to the New Pete's Run trunkline (T-
3). Table 86 gives the fractions of total flow, metals, and cyanide in New
Pete's Run represented by the sum of the mean daily discharges from these
three point sources, as given in Tables 65, 66, and 67.
It suggests the possibility of other (unidentified) point sources
discharging Cd, Cr, Ni, and CN to the trunkline. The high mean Cr flow in New
Pete's Run is primarily the result of an extremely high flow on one of the
three days the trunkline was sampled. An alternative hypothesis (to an
unidentified point source) could be a breakdown of the Point Source 3 Cr
treatment system during trunkline sampling. Table 87 presents a comparison of
random superposition pollutant flow limits for the three point sources with
maximum and minimum daily mean flows in New Pete's Run. This comparison
suggests the same conclusion stated above, that is, Cd, Cr, Ni, and CN are not
well accounted for by discharges from Point Sources 1, 2, and 3«
Tables 88, 89. and 90 give point source random superposition flow limit
comparisons for the Washington Street Feeder, Pete's Run Interceptor, and
South Northside Interceptor, respectively. The Washington Street Feeder
receives discharges from two electroplating shops (Point Sources 4 and 5) and
a Zn galvanized fence production facility. Once again, the superimposed
maximum and minimum point source Cd discharge rates are substantially lower
than the observed feeder line flow limits. The relatively high Cu and CN
feeder line flows may be due to a batch dump of a Cu-CN plating solution
161
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TABLE 86. FRACTIONS OF WASTEWATER, METALS, AND CYANIDE FLOWS IN
NEW PETE'S RUN TRUNKLINE ATTRIBUTABLE TO POINT SOURCES
1 , 2. AND 3
Total FlowPounds Per Day
(mgd) ~Cd£7Ni Pb Zn Cu CNP
0.96 0.26 0.18 0.30 0.83 3-4 0.76 0.51
TABLE 87. RANDOM SUPERPOSITION FLOW LIMITS FOR METALS AND CYANIDE
IN COMBINED POINT SOURCES 1, 2, AND 3 EFFLUENT
Parameter
Cd
Cr
Ni
Pb
Zn
Cu
CN-
Combined
Upper
0.95
0.31
1.48
0.42
48.3
12.2
2.95
Flow Limits
Sources
Lower
0.70
0.17
0.78
0.16
19.6
5.81
0.98
(Ibs/day)
New Pete's
Upper
3.62
2.52
3-99
0.33
14.5
15.8
9.07
Run Int.
Lower
2.62
0.22
2.52
0.26
6.38
9.06
3.35
TABLE 88. RANDOM SUPERPOSITION FLOW LIMITS FOR METALS AND
CYANIDE IN COMBINED POINT SOURCES 4, 5, AND 7
EFFLUENT
Flow Limits (Ibs/day)
Combined Sources Washington Feeder
Parameter Upper Lower Upper Lower
Cd
Cr
Ni
Pb
Zn
Cu
CN-
0.94
143.0
7.36
0.61
92.3
4.23
.038
0.36
45.4
3.72
0.12
15.8
1.25
.030
2.58
38.9
4.32
0.33
87.9
13.1
16.3
1.54
28.2
1.83
0. 19
30.7
2.64
1.08
162
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TABLE 89- RANDOM SUPERPOSITION FLOW LIMITS FOR METALS AND
CYANIDE IN COMBINED POINT SOURCES 9 AND 10 EFFLUENT
Flow Limits (Ibs/day)
Combined SourcesPete's Run Int.
Parameter Upper Lower Upper Lower
Cd
Cr
Ni
Pb
Zn
Cu
CN-
O.QOG25
0.65
11.7
0.033
1.7
0.33
0. 19
0.002
0.37
5.44
0.031
0.89
0.19
0.16
0.0067
0.24
0.95
0.80
6.86
2.98
0.40
0.018
0.18
0.45
0,54
2,. 6
1.7
0.072
TABLE 90. RANDOM-SUPERPOSITION FLOW LIMITS FOR METALS AND CYANIDE IN
COMBINED POINT SOURCES 8 AND 12 EFFLUENT '
Flow Limits (Ibs/day)
Combined Sources South Northside Int.
Parameter Upper Lower Upper Lower
Cd
Cr
Ni
Pb
Zn
Cu
CN-
0.0015
7.35
0.11
0.16
2,36
19.8
0.21
0.0015
1.98
0.22
0.068
0.21
3.2
0.17
0.011
0.416
0.087
0.12
11.9
1.61
0.089
0.001
0.14
0.045
0.069
2.27
0,61
0.013
during Day 3 (Table 83). The Pete's Run point source-trunkline flew limit
comparison indicates that interceptor Zn and Cu flows are not accounted for by
Point Sources 9 and 10 combined discharges. The high Ni discharge is from
Point Source 9i evidently related to the production of Ni-based alloys during
the sampling period. Finally, the South Northside Interceptor-point source
flow comparison indicates that all interceptor metal flows, except Zn, are
accounted for by Point Sources 8 and 12. Inspection of Table 72 indicates a
significant and highly variable Zn discharge from Point Source 8. This
suggests that the high interceptor Zn flows may result from a process solution
batch dump or markedly increased production activity at Point Source 8 during
Day 2 of interceptor sampling (Table 66).
163
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RESULTS AND DISCUSSION
The primary focus of this work was to determine flow characteristics of
heavy metals and cyanide in the Kokomo waste treatment system. Major elements
of the flow picture include discharges from point sources served by the
collection system, movement within the collection system that reflects the
existence of both point and area sources, and fates of metals entering the
system. Emphasis was placed on concentrations in sludge and resulting
limitations on sludge disposal options. Table 91 compares metal
concentrations measured in Kokomo sludge cake and estimates concentrations
related to trunkline flows and point source discharges.
Cadmimum
Point source discharges of Cd account for little more than half of that
found in sludge cake and less than 20 percent of combined trunkline flows.
Inspection of Tables 65 through 77 indicates that only Point Sources 2, 3, and
5 show significant Cd discharges. Tables 80 and 81 indicate that virtually
all Cd trunkline flow is observed in the North Northside and New Pete's Run
Interceptors. These trunklines serve, respectively, Point Source 5 (North
Morthside) and Point; Sources 2 and 3 (New Pete's Run).
This strongly suggests that the significant Cd point sources have been
identified, and that trunkline sampling was carried out at a time when Point
Sources 2, 3, and 5 were discharging higher than average amounts of Cd, while
point source testing was conducted during periods of relatively low discharge.
In support of this contention, the Cd plating line at Point Source 5 operates
only periodically and at differing levels of activity (area plated/hour).
Cadmium flow in the Washington Street Feeder which receives Point Source 5
waste (Table 83) averages 2.16 Ibs for three sampling days. This is very
close to the 2.2 Ibs flow seen in the North Northside Interceptor on sampling
Day 3-
It is recommended that further sampling be conducted at Point Source 2,
3, and 5 to characterize their discharges and identify other point sources of
Cd over a longer period than the three days of this study. If this fails to
account for Cd observed in the POTW sludge, it is recommended that trunkline
sampling be conducted in the North Northside Interceptor upstream from, and as
close to, the Washington Street Feeder junction as reasonable access permits.
Chromium
Unlike Cd, point source discharges more than account for Cr flows
observed in major trunklines, and both result in substantially larger
projected Cr concentrations in POTW sludge than have been measured. Thus no
supplementary source or trunkline monitoring are necessary for source
identification purposes. Approximately 95 percent of the Cr entering the POTW
flows from the North Northside Interceptor (Table 81). Table 83 indicates
that of the three feeder lines discharging to this interceptor, the Washington
Street line accounts for 99 percent, i.e., 31-3 Ibs/day. This in turn
represents 82 percent of the average flow detected during the interceptor
sampling period.
164
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TABLE 91. COMPARISON OF METAL CONCENTRATIONS IN SLUDGE CAKE
Sludge Metal Concentraation (mg/kg dry wt.)
Basis of Projection Cd Cr Ni Pb Zn Cu CN~
Sludge cake analysis 377 1,060 533 13,600 1,790
Trunkline flow* 1,100 7,270 550 600 14,100 3,230 1,580
Point source discharge* 202 16,400 830 280 100,000 3,760 1,380
* Based on per capita sludge generation rate of 0.12 Ibs/day (dry wt.),
and POTW metal removal rates determined in, "A Mass Balance of Several
Heavy Metals Around an Operational Activated Sludge-Gravity Filter
Municipal Sewage Treatment Plant," by Bert Michalczyk.
Point Sources 4 and 5, two electroplating facilities, are served by the
Washington Street feeder. The sum of the average Cr discharges^ observed
during their respective monitoring periods is approximately 92 Ibs/day, with
83-2 Ibs/day originating with Point Source 5. Installation of a Cr reduction
unit, followed by pH adjust and clarifier steps at Point Source 5, would
achieve the greatest reduction in Cr discharges to the POTW. A modest 90
percent treatment efficiency at Point Source 5 would reduce the POTW sludge Cr
concentration by an estimated 92 percent to a level of approximately 90 mg/kg.
Nickel
The POTW sludge-cake analysis and projected sludge Ni concentration based
on trunkline monitoring are virtually the same. The sum of the point source
discharges gives a projected source-related sludge Ni concentration more than
50 percent higher. Thus there is no indication that- further trunkline or
source sampling are required to identify sources of Ni to the system, other
than those sampled in this work.
Of the 9.6 Ibs/day Ni flow observed in the total of the six major
trunkline average flows, 5.1 Ibs were seen in the North Northside Interceptor
and 3.6 Ibs in the New Pete's Run Interceptor (Table 81). Table 83 shows a
highly variable Ni flow in the North Northside Washington Street feeder which
averages 2.92 Ibs/day. The Washington Street feeder receives discharges from
Point Sources 4 and 5. The latter discharged an average of 4.8 Ibs/day of Ni
during the three-day source monitoring period. This compared closely with,
and would appear to account for, the 5.1 Ibs/day average flow seen in the
North Northside Interceptor.
New Pete's Run Interceptor receives discharges from Point Sources 1, 2,
and 3. Inspection of Tables 65, 66, and 67 indicates that while Point Sources
1 and 3 are significant dischargers of Ni, the sum of their daily average
discharges is less than 1 Ib/day, which represents less than 30 percent of the
average daily flow observed in New Pete's Run. Of the other major trunklines,
165
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only Pete's Hun, which serves Point Sources 9 and 10 upstream from the
trunkline sampling location, exhibits a significant Ni flow. Tables 73 and 75
indicate that Point Source 9 discharged a daily average of 8.4 Ibs/day during
a three-day monitoring period, i.e., almost 55 percent of the total Mi
discharges observed during the entire point source monitoring program. A
summary of Point Source 9 waste treatment system performance in Table 7U
suggests that the relatively high Mi discharge is a consequence of an
extremely high Ni concentration in the raw (untreated) waste, i.e., in the
range of 900 to 1,500 mg/1.
Based on this information, it would appear that Point Sources 1, 3. 5,
and 9 are the primary point source dischargers of Ni to the collection system.
Although the point source and trunkline monitoring for the Pete's Run and New
Pete's Run Interceptors did not exhibit good correlation between source
discharges and trunkline flows of Ni , further monitoring to identify other
point sources does not appear necessary.
A strategy to reduce Ni discharges to the POTV would include installation
of a pH adjust step and a clarifier at Point Source 5, and a change in the
Point Source 9 waste treatment system to optimize Ni removal from the Ni-rich
raw waste. This could involve either a segregated Ni treatment system, or an
upward shift of clarifier pH toward the Ni minimum solubility value of
approximately 10,
Lead
The metals balance conducted on the Kokomo POTW was not completed for Pb
due to analytical difficulties encountered in the project laboratory.
Projected Pb concentrations in sludge cake resulting from trunkline flows and
point source discharges are 600 mg/kg and 280 mg/kg, respectively (Table 91 )
Table 81 indicates that the North Northside Interceptor accounts for 66
percent of the trunkline flow, Pete's Run Interceptor, 17 percent, and the New
Pete's Run Interceptor, 8 percent. Table 83 exhibits 0.36 Ibs/day total Pb
flow for the three major North Northside Interceptor feeders, i.e.
substantially below the interceptor Pb flow (Table 84). A survey of Tables 65
to 77 indicates significant discharges from Point Sources 3, 5t 6, and 12.
All but Point Source 12 discharge to one of the three trunklines for which
significant Pb flows were detected.
The probable explanation for the twofold difference between trunkline Pb
flows and source discharge rates is metal entering the combined storm-sanitary
collection system during coincident trunkline sampling and precipitation
events, or pavement runoff which is resuspended during high-flow trunkline
sampling periods immediately after precipitation events. Table 79 indicates
an average Pb concentration of 810 mg/kg in Kokomo pavement dust. The bulk of
this is presumed to originate with automotive exhaust gases from vehicles
burning leaded gasoline. Table 79 exhibits total Pb loadings in pavement dust
per curb mile, with an average of 1.2 Ibs of Pb per curb mile. Since the
combined storm-sanitary system serves approximately 100 curb miles, the runoff
of even a small fraction of street dust in a major precipitation event would
more than account for the trunkline flow-point source discharge discrepancy.
166
-------
With this in mind, no supplementary trunkline or point source sampling is
required to account for Pb inputs to the system. As vehicles burning leaded
fuel are retired from service, POTW Pb input will presumably decrease.
Zinc
Close agreement between the measured sludge-cake Zn concentration and the
projected concentration based on trunkline flow measurements is shown in Table
91. Note that the. sum of the average daily Zn discharges from the twelve
point sources is a factor of seven higher, so there is evidently no further
sampling required to identify sources of Zn to the Kckomo treatment system. A
survey of Tables 65 to 77 indicates that Point Sources 3, U, 6, and 7 are the
major Zn dischargers. Table 70 exhibits an extremely high Zn discharge for
Point Source 6 the first sampling day. In particular, this single-day Zn
discharge constitutes 60 percent of the sum of the daily average discharges
for all twelve point sources monitored. Inasmuch as Point Source 6 is a steel
remelt, wire-fence-fabricating facility, the likely explanations are the
processing of scrap rich in Zn galvanized material, or a flotation problem in
the plant clarifier (Figure 50), or both.
Significant reductions in Zn discharges to the Kokorao treatment system
could be effected by running a series of jar tests (metal solubility vs. pH)
on Point Source 6 clarifier solution to determine an optimum pH for Zn
precipitation. This same protocol could be used to reduce Zn discharges from
Point Sources 3 and 4, though changes in clarifier pH in these cases would
represent compromises between Zn and Cu, and Zn and Cr, respectively.
Finally, Point Source 7 (a galvanizing operation) should be required to
install a pH adjust and clarifier system to remove Zn from process water
discharged to the municipal system.
Copper
The sum of the point source discharges of Cu is in close agreement with
the cumulative trunkline flow, and both result in a projected Cu concentration
in sludge cake which substantially exceeds measured values (Table 91). The
primary dischargers of Cu to the Kbkomo treatment system are Point Sources 2,
3, 7, and 12. Point Sources 2 and 3 are electronics/semiconductor and circuit
board-producing facilities with waste treatment systems in operation. They
account for 35 percent of the Cu discharged to the municipal system. Since
Point Source 2 discharges no other metals at rates comparable to Cu, clarifier
pH at this facility could presumably be optimized for Cu precipitation to
effect a discharge reduction. Optimizing the Point Source 3 treatment system
pH for Cu removal must be undertaken with some care to insure that removal of
other metals, notably Cd and Zn, is not unduly compromised. Since neither
Point Source 7 (Zn galvanizing facility) nor Point Source 12 (printing plant)
has treatment systems, installation of properly sized pH adjust-clarifier
systems at these sites would substantially reduce their Cu discharges.
A comparison of trunkline Cu flows (Tables 80 and 81) with point source
discharges (Tables 65 to 77) reveals a lack of correlation between them. In
particular, the Fayble trunkline exhibits a significant Cu flow, although
there are no known point sources discharging to it. Further, Cu flow in
167
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Pete's Run Interceptor averaged 2.5 Ibs/day, while Point Sources 9 and 10
which discharge to it account for only 0.27 Ibs/day. Thus further monitoring
of Point Sources 9 and 10 discharges is in order to determine if they can
account for Cu flows in the Pete's Run Interceptor. If not, then
supplementary trunkline sampling would be called for above the Old Park Road
feeder function. Further, the Fayble trunkline contributes a projected 210
mg/kg Cu to the POTW sludge cake concentration. If the Cu discharge reduction
measures outlined previously do not reduce Cu concentrations sufficiently for
disposal purposes, it might be necessary to embark on a trunkline sampling
program in order to locate the source(s) responsible for the observed metal
flow.
Cyanide
No cyanide analyses were performed on Kokomo sludge cake. As indicated
in Table 91, the projected sludge CN concentrations based on trunkline and
source monitoring results are 1,580 and 1380 mg/kg, respectively. Since the
sum of the point source CN discharges is within 12 percent of measured
trunkline flows, no further sampling is deemed necessary to identify sources.
This conclusion is also based on the fact that, except for sampling Day 3 on
the Fayble trunkline,- the only substantial CN flows were detected in the North
Northside and New Pete's Sun Interceptors (Tables 80 and 81).
A survey of Tables 65 to 77 shows that both of these trunklines receive
substantial discharges from monitored point sources, i.e.. Point Sources 5 to
North Northside and Point Source 3 to New Pete's Run. Note in Table 83 the
high CN flow in the Washington Street feeder on sampling Day 3- This suggests
that Point Source 5 was dumping a cyanide plating solution at that time. This
contributed 5.4 Ibs/day to the daily average CN flow in the Washington Street
feeder, and represents 66 percent of the total CN flow detected in the six
major trunklines. Substantial reductions can be made in CN discharges to the
municipal system through installation of a CN destruct system at Point Source
5 and improvement in the efficiency of the CN destruct unit at Point Source 3-
168
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Malaney, G. W., W. D.;Sheets, and R. Quillin. Toxic Effects of Met-allic Ions
on Sewage Microorganisms. Sewage and Industrial Wastes, 1959-
McCabe, L. Survey of Community Water Supply Systems. Journal of the American
Water Works Association, 1970.
McCaull, J. Building a Shorter Life. Environment, 1971.
McDermott, G. N. Zinc in Relation to Activated-Sludge and Anaerobic Digestion
Processes. Proceedings of the 17th Industrial Waste Conference, Purdue
University, West Lafayette, Indiana, 1962.
McDermott, G. N., M. A. Post, B. N. Jackson, M. B. Ettinger. Nickel in
Relation to Activated-Sludge and Anaerobic Digestion Processes. Journal
Water Pollution Control Federation, 37:163-177, 1965.
McDermott, G. N., W. A. Moore, M. A. Posa, M. B. Battinger. Effects of Copper
on Aerobic Biological Sewage Treatment. Journal Water Pollution Control
Federation, 35:227-241, 1963.
McKee, J. £., and H. W. Wolf. Water Quality Criteria. State Water Resources
Control Board, California, 1963-
Metcalf and Eddy, Inc. Wastewater Engineering: Treatment, Disposal, Reuse.
2nd ed. New York: McGraw-Hill Book Company, 1979.
Moore, W. A., G. N. McDermote, M. A. Post, J. W. Mandia, M. B. Settinger.
Effects of Chromim on the Activated-Sludge Process. Journal Water
Pollution Control Federation, 33:54-72, 1961.
Neufeld, R. D. Heavy Metals-Induced Deflocculation of Activated Sludge.
Journal Water Pollution Control Federation, 48:1840-1947, 1976.
172
-------
Neufeld, R. D.t J. Gutierrez, and R. A. Novak. Kinetic Model and Equilibrium
Relationship for Heavy Metal Accumulation on Activated Sludge. Journal
Water Pollution Control Federation, 49: 489-498, 1977.
Neufeld, R, D.,'and E. R. Hermann. Heavy Metal Removal by Acclimated Activated
Sludge. Journal Water Pollution Control Federation, 47:310-329, 1975.
Newcomb, R. C. Quality of the Groundwater in Basalt of the Columbia River
Grup, Washington, Oregon, and Idaho. Geological Survey Water Suply Paper
1999-N. Washington, D.C.: U.S. Government Printing Office, 1972.
Newell, I. L. Mercury nd Other Heavy Metals in Water Supplies. New England
Water Works Association Journal, 1971.
Nomura, M. M., and R. H. F. Young. Fate of Heavy Metals in the Sewage
Treatment Process, University of Hawaii, Honolulu, Hawaii, 1974.
Oliver, B. G., and E. G. Cosgrove. The Efficiency of Heavy Metal Removal fay a
Conventional Activated Sludge Plant. Water Research, 3:869-374, 1974.
Olthof, M. Heavy Metal Contamination of Organic Sludges. Paper presented at
the 51st Annual Conference of the Water Pollution Control Federation,
Anaheim, California, 1978.
Olver, J. W., W. C. Kreye, and P. H. King. Heavy Metal Release by Chlorine
Oxidation of Sludges. Journal Water Pollution Control Federation, 1975.
O'Neill, J. The Effects of Copper and Zinc on Mesophilic Digestion of Sewage
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173
-------
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Indianapolis, Indiana, 1977.
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Works Journal, 1946.
Salotto, B. V. Organic Load and Toxicity of Copper to ActivatedSludge
Process. Proceedings of the 19th Industrial Waste Conference, Purdue
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1958.
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1959a.
-------
Stones, T. The Fate of Zinc during the Treatment of Sewage. Ibid., Part 2,
1959b.
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»
U.S. Environmental Protection Agency. Sludge Treatment and Disposal, Sludge
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U.S. Federal Register. Title 40, Sec. 403. Final Rules, 1978.
Water Pollution Control Federation. Wastewater Treatment Plant Design; A
Manual of Practice. Water Pollution Control Federation, Washington, D.C.,
1977.
Whipple, W., Jr., and J. V. Hunter. Nonpoint Sources and Planning for Water
Pollution Control. Journal Water Pollution Control Federation, 1977.
Wilber, W. G., and J. V. Hunter. Heavy Metals in Urban Runoff. Non-Point
Sources of Water Pollution-Proceedings of a Southeastern Regional
Conference. P. M. Ashton and R. C. Underwood, eds. Virginia Water
Resources Research Center, Blacksburg, Virginia, 1975.
Wischmeger, W. J., and J. T. Chapman. A Study of the Effect of Nickel on
Sludge Digestion. Sewage Works Journal, 19:790-795, 1947.
175
-------
APPENDIX A
MODIFICATIONS OF EPA
TOTAL METALS METHODOLOGY
The SPA method for total metals was modified slightly in three ways to
facilitate rapid analysis of samples. One change was the addition of 5 ml
rather than 3 ml of HNO-j to the aliquot being evaporated. It was found that
this quantity of acid greatly enhances dissolution of any oil or grease which
might be present and which "burns" the glass if not removed or dissolved.
Second, the digested sample was not filtered to remove silicates prior to
analysis. This was mainly a time-saving step but was justified on the basis
that the samples were not analyzed immediately, thus allowing .insoluble
material to settle. If care is taken to aspirate only from the top portion of
the sample, clogging of the atomizer is prevented.
A 90-minute digestion time for both the nitric and hydrochloric acids was
chosen in deference to the EPA method of digesting to a light-colored residue
in order to speed up analysis. The justification is based on an investigation
carried out to determine the effect of both HNO, and HC1 digestion times. In
summary, the procedure:
(1) digests 10 samples for a fixed length of time using nitric acid (90
minutes) followed by varying periods of hydrochloric acid digestion
(0, 30, 60, 90, 120, 180, 2UO minutes).
(2) digests 10 samples for varying lengths of time using nitric acid (0,
30, 60, 90, 120, 180, 240 minutes) followed by a fixed (90-minute)
hydrochloric acid digestion.
The results presented in Table A-1 and Figures A-1 and A-2 indicate that the
length of time of the HNO-s digestion has a greater effect than does the length
of time of the HC1 digestion. At a 90-minute HNO, digestion time, the metal
level reported was always near the average as opposed to the metal level
reported at other times. And since there was no discernible trend in the
data, a 90-minute digestion time was chosen for HNOs- For convenience, a 90-
minute period was also chosen for HC1 digestion.
176
-------
TABLE A-l. RESULTS OF INVESTIGATIONS OF HNO. AND HC1 DIGESTION TIME
TTAtJT AT"Tn\TC J
VARIATIONS
Length, of Time-,
of HG1 Digestion"
(rain. )
1
0
30
60
90
120
180
240
Cd
0.220
0.2i(.9
0.219
0.2^0
0.237
0.200
Metal
Cr
0.969
1.01
1.07
1.00
0.968
0.905
Cone.
Cu
0,614
0.702
0.612
0.652
0.701
0.606
(mg/1)
Hi
1-51
1.44
1.58
1.60
1.49
1.38
£n
7.34
7.28
7.63
7.24
7.44
6.70
90 min. ELTO^ digestion time.
Length, of Time
of HN03 Digestion^
(rain. )
2
0
30
60
90
120
180
214.0
Cd
0.273
0.338
0.314
0.316
0.264
0.320
0.328
Ketal
Cr
1.07
1.23
1.09
1.07
0.980
1.08
0.943
Cone.
Cu
0.977
1.03
0.781
1.03
1.04
1.24
1.12
(Dlg/1)
Ni
1.92
1.58
2.08
2.19
2.09
2.17
1.82
2In
lO.k
11.4
11.1
11.6
10.1
15.6
10.4
90 min. HC1 digestion time.
177
-------
15.6
00
c
o
c
0>
u
c.
o
o
0»
z e.
*
o
f*
l_
o
XI
O
60 120 180
Length of HN03 Digestion (min)
12.0
O
*»-
a
o
o t
o *-*
c
N
3.0
240
Figure A-l. Effect of various HNO digestion times on metal concentrations,
-------
2.0
(A
O
c
2
i
c
N
Figure A-2. Effect of various HCI digestion times on metal concentrations,
-------
APPENDIX B
OPERATIONAL SETTINGS
FOR PERKIN-ELMER ATOMIC
ABSORPTION SPECTROPHOTOMETERS
During this study, two atomic absorption spectrophotometers were used: a
Perkin-Elmer 306 and a Perkin-Elmer 603. Although the machines were different
in appearance, fundamental controls were the same, thus allowing only one
explanation of the setting used.
A detailed discussion of atomic absorption spectrophotometry is
impossible in this report, however, the fundamental control variables need
explanation. These can alter the results obtained mainly through spectral and
other interferences.' These variables are wave length, slit width,- fuel-air
ratio, burner height and orientation, and energy output of the intrument. The
proper setting of each of these is listed in Table B-1 for each element.
In brief, each element absorbs light of a characteristic wave length and
the machine must be tuned to that particular wave length, even ^though a
specific element lamp is used. That lamp, while emitting the desired wave
length, also emits others which are unnecessary and which can interfere with
analyses. The slit width controls the width of the spectral band about the
desired wave length. A narrower band is necessary for an element with closely
spaced, intense spectral lines. The fuel-air ratio affects the temperature of
the flame, and hence excitation of the element in question. For example, an
easily excited element like chromium must be done with a cooler flame to avoid
interferences. The burner orientation should be arranged so that the light
beam passes over the entire length of the burner and the height should
maximize absorbance. The energy output is a measure of the energy added
through the photomulitiplier tube that serves as an amplifier for the
detection device. This should be set in such a way that the reading never
goes off-scale.
180
-------
TABLE B-l. OPERATIONAL DATA OF THE ATOMIC ABSORPTION SPECTROPHOTOMETE5..
Element
Cd
Cr
Cu
Ni
Zn
Pe
Pb
Wavelength.
228.5 nm
357.9 run
3 21;. 7 nm
232.0 nm
213.9 ran
372*0 run
283.3 nm
Slit Width
1^
k
k
3
k
3
I;
Flame
oxidizing
reducing
oxidizing
oxidizing
oxidizing
oxidizing
oxidizing
oxidizing - fuel lean
reducing - fuel rich
In all cases the fuel is acetylene and the oxidant is air,
181
-------
APPENDIX C
CALCULATIONS TO DETERMINE
FLOW RATES OF THREE SELECT STREAMS
IN THE KOKOMO, INDIANA, TREATMENT PLANT
RAS AND WAS FLOW MEASUREMENT CONCEPTS
The flow rates of waste-activated sludge and return-activated sludge were
determined using a series of pump characteristic curves supplied by Allis-
Chalmers, the manufacturer of the six pumps used. These pumps were powered by
variable frequency drives (VFD) which vary the impeller speed to obtain
various flow rates. After about Day 10, however, the pumps were only run at
100 percent capacity because of the treatment plant management's feeling that
using the VFD caused excessive operational and maintenance problems. Meters
were only available indicating the percentage of the maximum impeller speed at
which the pumps were operating. Only after project completion were the flow
meters made operational. This posed some problem in compositing samples
during the first ten-day period; to do so entailed assuming a linear
proportional decrease of flow rate with percentage of maximum. As will- be
seen later, this was a valid approximation.
This method basically involved using the curves supplied by Allis-
Chalmers, specific- for these pumps and which showed the total head as a
function of flow rate with impeller speed as a parameter. This graph is shown
in Figure C-1. The static head was calculated from elevations obtained from
construction plans for the plant. When the flow meter was finally put in
operation, one operating point was obtained, that is, at 4,200 gpra the total
head was 32.9 ft, as determined from Figure C-1. The dynamic head was then
calculated as the difference between the total and static heads. This head is
proportional to the flow rate squared, allowing calculation of the
proportionality constant. Knowing this, the head could be calculated for any
flow rate and operating lines plotted, as in Figure C-1. To then determine
the flow rate associated with a given pump setting, it is necessary to
calculate the percent of the rated impeller speed for each of the parametric
curves. The intersection of these curves and the operating line shows the
total head and the desired flow rate for that speed. The calculations
necessary for this are presented below. Figure C-2 is a plot of flow rate
versus pump speed for the RAS and WAS pumps. Note the agreement between these
and the assumed linear curve used for compositing the samples at the higher
values used.
182
-------
00
la
a>
X
o
60
40 -
20 -
I-II8O RPM
2-1080 RPM
3-980 RPM
4 880 RPM
5-780 RPM
6 680 RPM
RAS Operating
line
WAS Operating
line
1000
2000
3000
4000
5000
Flow Rate Gallons per Minute
Figure C-l. Pump characteriatic curves and operating lines for RAS and WAS pumps.
-------
00
Q.
0>
Q>
*
a
a:
c>
u_
4OOO -
30OO
2000
IOOO - -
4200 at 100%
100
Percent of Rated Impeller Speed
Figure C-2. Flow rate as a function of percent of rated impeller speed for HAS and WAS pumps.
-------
HAS and WAS Flow Measurements Calculations
Static Head WAS RAS
Elevations (ft above datum)
From 792.33 787.10
To 801.50 792.33
Difference 9.17 5.23
Dynamic Head
(32.9 - Static Head) 23.7 27.7
Bernoulli's Equation:
V^ P V^ P
^ + + Z. + h_ - TT- + + Z, + h
2g p 1 L 2g p 2 p
Simplifications: ?1 = ?2 - 1 atm
V1 = V2 = 0
Therefore ;(Z1 - Z2) + hrw = hp
This implies that the dynamic head is composed solely of head losses arising
from.piping, such as friction, valves, and so on. These all are proportional
to I_ and, therefore, to Q2 for a given pipe diameter. Thus:
2g
hp s (ZT - Z2) + KQ2
(Q in gpm, hp in ft)
Using the given point as explained above:
WAS 32.9 = 9.17 + k( 4200)2
RAS 32.9 = 5.23 f k(4200)2
kWAS = 1-35 x TO'6
Table C-1 develops the curve of h versus Q for the WAS and RAS pumps
according to the above equation. These are plotted and identified in Figure
C-1.
The intersection of the pump curve with the operating line determines the
flow rate at the operating speed. These are plotted for the six given speeds,
expressed as a percentage of the maximum speed for the WAS and RAS pumps in
Figure C-2.
185
-------
TABLE C-1. DEVELOPMENT OF TOTAL HEAD
VERSUS FLOW RATE CURVE FOR
WAS AND HAS PUMPS AT
KOKOMO, INDIANA
Flow Rate
(gpm)
4200
4000
35CO
3000
2500
2000
"1000
0
Total Head
WAS
32.9
30.8
25.7
21.3
17.6
14.6
10.5
9.2
(ft)
HAS
32.9
30.4
24.5
19.4
15.0
11.5
6.8
5.2
VACUUM FILTER FILTRATE FLOW MEASUREMENT
The concept involved in measuring the stream flow is fairly simple: the
mass of water in the filtrate stream must equal the difference in the mass of
water in the vacuum filter feed and sludge cake streams. It is necessary to
consider the solids concentration because they are not negligible at these
high concentrations. The mathematical development is:
(1) #H20 Filtrate = #H20 Vacuum Filter Feed - #H2° Cake
Water in vacuum filter feed
(2) #H2o in VFF = (QVFF) (8.34) (SSL) (1 - fS)
where QVFF = Volume of vacuum filter feed as determined by stroke counter
on piston pump
8.32 = Ibs sludge/gal for specific gravity of 1.0
= Specific gravity of sludge in VFF
fS = Fraction of solids in VFF
186
-------
In general, when there are two constituents of different specific gravity
(3)f-fUf
Sl Sl S2
Therefore:
(4) _1_ , -JS_ (1
\.*+/ e q 10
SSL SSOL, -1-0
where fS = Fraction of solids
SSOL = sPecific gravity of the solids
1.0 = Specific gravity of water
Also:
,-. 1 , fVS " (1-fVS)
wA "c 10 25
SSOL 1>0 ^
where fVS s Fraction volatile solids
1.0 s. Specific gravity of volatile solids (1)
2.5 = Specific gravity of fixed solids (2)
From Kokomo lab data: fVS s 0.425, fS = 0.148.
Therefore :
1 0.425 . C1-Q.425)
= * ; T 25
SSOL X 2'5
And:
1 _ 0.148 , (1-0.148)
(9) S
Therefore:
CIO) #H20 in VFF » CQVFT) C8.34) (1.054) (1
187
-------
(11) #H20 in VFF s (QVFF) (7-^)
Water in filter cake:
(12) #H2o Cake = (//sludge cake) (1 - fSc)
where fSr = Percent solids in filter cake
Volume of filtrate:
#H.O Filtrate
(13) Q
F (1-fS) (3.34) (SSLp)
where fS = Percent solids in filtrate
= Specific gravity of filtrate
fs Ci-fs,)
a4) ^_ a ^L_ +
aSLF SOLF 1048)
SSLF 1*36 1'°
(19) SSLF - 1.01
188
-------
Therefore :
#H-0 Filtrate
(20) QF " (1-0.043) (8.34) (1.01)
#H-0 Filtrate
<21> QF ' - 02 -
where #H2o Filtrate = #H20 in VFF - #H20 cake
Equation (-11) Equation (12)
This calculation, Equation (21), was done each day the vacuum filter was
on-line using the total feed volume, cake volume, and the average fraction of
solids in the cake for that day.
189
-------
APPENDIX D
POINT SOURCE MONITORING TABLES
Tables D-1 through D-38 contain flows and pollutant concentrations
obtained in the point source monitoring program. Samples were collected for
each trunkline at 2-hour intervals for three 2U-hour periods.
190
-------
~ JT1~ -- -~7..-- ..-,.--. -i * -- - - " '' " ' " ...... .. . ' - " ' - - -..-..
DAY OF
DATE WEEK TIME
3-12-79 M 6P
8P
10P
3-13-79 T 12A
2A
4A
M 6A
" 8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
Mfin
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
042
042
042
044
042
026
033
046
046
046
041
046
041
006
496
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.002
.002
.002
.001
.001
.002
.002
.003
.002
.001
.001
.001
.002
.001
METAL AND CYANIDE CONCENTRATIONS
(rog/D
Cr Nl Pb Zn Cu
0.005
0.005
0.007
0.013
0.005
0.020
0.005
0.017
0.005
0.006
0.009
0.008
0.009
0.005
0.08
I i
0.09
0.08
0.06
0.05
0.05
0.07
0.07
0.07
0.07
0.06
0.05
0.07
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.02
.03
.05
.04
.03
.03
.03
.05
.03
.03
.04
.03
.03
.01
1.01
1.07
0.97
0.83
0.59
0.73
0.70
0.69
0.68
0.70
0.50
0.51
0.75
0.18
0.071
0.072
0.056
0.033
0.028
0.036
0.050
0.180
0.050
0.034
0.041
0.023
0.050
0.024
CN~
<0.10
<0.10
-------
TABLE D-2. POINT SOURCE 1. SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
3-13-79 T 6P
8P
10P
3-14-79 W 12A
2A
4A
£ 6A
N>
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
042
018
013
014
004
033
041
042
042
042
042
046
032
015
379
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.001
.001
.001
.002
.002
.001
.001
.001
.001
.001
.001
.001
.001
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.007
0.012
0.004
0.011
0.010
0.006
0.007
0.004
0.006
0.005
0.004
0.004
0.007
0.003
0.048
0.047
0.013
0.012
0.009
0.059
0.073
0.057
0.074
0.070
0.045
0.055
0.047
0.023
0.04
0.03
0.02
0.01
0.02
0.04
0.03
0.03
0.03
0.03
0.03
0.02
0.03
0.01
0.53
0.45
0.17
0.14
0.10
0.37
0.46
0.37
0.46
0.49
0.52
0.52
0.38
0.15
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
032
064
075
151
169
077
042
061
050
049
029
033
069
045
CN~
<0.10
<0.10
<0.10
0.10
-------
/
i
TABLE D-3. POINT SOURCE 1,
SAMPLING DAY
THREE
DAY OF
DATE WEEK TIME
3-14-79 W 6P
8P
10P
3-15-79 TH 12A
2A
4A
g 6A
8A
10P
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
041
020
013
033
042
042
041
042
042
042
042
046
037
010
446
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr
0.009
0.004
0.006
0.009
0.011
0.010
0.006
0.005
0.014
0.015
0.014
0.012
0.010
0.004
Nl
0.06,
0.03
0.01
0.06
0,07
0.07
0.06
0.08
0.07
0.05
0.05
0.05
0.05
0.02
Pb
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.04
0.03
0.01
0.02
0.01
Zn
0.54
0.45
0.14
0.44
0.40
0.44
0.43
0.30
0.60
0.35
0.35
0.11
0.38
0.14
Cu
0
0
0
1
0
0
0
0
0
0
0
0
0
0
.029
.073
.045
.172
.023
.017
.030
.042
.025
.070
.016
.018
.130
.329
CN
0.12
o.io
o.io
-------
TABLE D-4. POINT SOURCE 2. SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
7-5-79 Til 12P
2P
4P
6P
8P
u>
is 10P
7-6-79 FRI 12A
2A
4 A
6A
8A
10A
MEAN
STANDARD DEVIATION
MGD
LHS/DAY
MILLION GAL,
OF FLOW/ 2 H
0.072
0.072
0.072
0.072
0.072
0.072
0.072
0.072
0.072
0.072
NF*
NF
0.072
0.000
0.720
»
Cd
0.068
0.032
0.042
0.035
0.048
0.015
0.030
0.024
0.017
0.010
-
-
0.032
0.018
0.19
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.022
0.018
0.037
0.016
0.016
0.007
0.013
0.021
0.018
0.015
-
-
0.018
0.008
0.11
0.03
0.02
0.04
0.02
0.03
0.09
0.03
0.04
0.01
0.01
-
-
0.03
0.02
1
0.19
0.03
0.01
<0.01
<0.01
<0.01
<0.0l
0.01
0.01
<0.01
<0.01
-
-
<0.02
0.01
<0.078
0.41
0.21
0.16
0.14
0.18
0.25
0.26
0.10
0.08
0.13
-
-
0.197
0.096
1.15
0.99
0.92
0.56
1.21
2.38
0.69
1.79
1.15
1.01
0.53
-
-
1.12
0.57
6.74
CN
-------
TABLE D-5. POINT SOURCE 2. SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
7-6-79 FRI 12P
2P
4P
6P
8P
£ 10P
7-7-79 SAT 12A
2A
4A
6A
8A
10A
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL.
OF FLOW/2H
0.027
0.027
0.027
0.027
NF*
NF
0.027
0.027
0.027
0.027
0.027
0.027
0.027
o.ooo
0.270
Cd
0.038
0.012
0.007
0.005
-
-
0,012
0.017
0.020
0.023
0.023
0.019
0.018
0.010
0.044
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.024
0.028
0.014
0.014
-
-
0.011
0.013
0.014
0.013
0.013
0.013
0.016
0.006
0.032
1 1
0.04
0.01
0.01
0.01
-
-
0.01
0.02
0.02
0.01
0.01
0.01
0.02
0.01
'
0.034
0.01
0.01
<0.01
<0.01
-
-
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.00
<0.027
0.20
0.07
0.06
0.03
-
-
0.12
0.18
0.19
0.12
0.09
0.10
0.12
0.05
0.26
1.04
0.57
0.28
0.25
-
-
0.63
0.90
1.12
1.22
1.28
1.00
0.82
0.37
2.16
CN
<0.10
<0.10
<0.10
<0.10
-
-
0.14
0.10
0.12
0.11
0.14
0.14
<0.12
0.02
<0.25
NF = No flow
-------
TABLE D-6. POINT SOURCE 2. SAMPLING DAY THREE
vo
DAY OF
DATE WEEK TIME
7-7-79 SAT 12P
2P
4P
6P
8P
10P
7-8-79 SUN 12A
2A
4A
6A
8A
10A
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
027
027
027
027
027
027
027
027
027
027
027
027
027
000
324
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.014
.011
.011
.010
.013
.017
.023
.023
.023
.035
.028
.034
.020
.009
METAL AND CYANIDE CONCENTRATIONS
(rng/1)
Cr Nl Pb Zn Cu
0.012
0.011
0.011
0.012
0.018
0.022
0.010
0.009
0.010
0.014
0.010
0.011
0.013
0.004
0.01
<0.01
0.01
0.02
0.01
0.02
0.01
0.01
0.02
0.02
0.01
0.01
0.01
0.01
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.00
0.07
0.07
0.14
0.22
0.17
0.14
0.18
0.14
0.13
0.16
0.14
0.13
0.14
0.04
0.78
0.65
0.62
Q.58
0.58
0.82
1.20
0.87
1.23
1.53
1.13
1.28
0.93
0.32
CN~
o.io
-------
TABLE D-7. POINT SOURCE 3, SAMPLING DAY ONE
"- "" ' ' - ,---, .,._.- . . - . _ - ,__.___ r ffl . { _.. __ B ^ ^ r. - .- . - J- __L -. L T--.T-J "_ .- ' . ..-.-_ - .__.__ ._ ^_ _
DAY OF
DATE WEEK TIME
7-2-79 M 6P
8P
10P
7-3-79 T 12A
2A
to 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL
OF FLOW/2H
0.173
0.173
0.173
0.173
0.173
NF*
NF
NF
0.171
0.171
0.171
0.171
0.172
0.11
1.549
*
Cd
0.050
0.070
0.056
0.020
0.040
-
-
-
0.045
0.068
0.072
0.076
0.055
0.018
0.71
METAL
Cr
0.015
0.009
0.009
0.010
0.009
-
-
0.008
0.009
0.011
0.008
0.010
0.002
0.13
AND CYANIDE CONCENTRATIONS
(mg/D
Nl Pb Zn Cu
0.04
0.04
0.04
0.03
0.03
-
-
-
0.04
0.06
0.07
0.07
0.05
0.02
0.59
i
<0.01
<0.01
<0.01
<0.01
<0.01
-
-
-
<0.01
0.01
<0.01
<0.01
<0.0l
0.00
;
<0.13
0.05
0.06
0.05
0.03
0.03
-
-
-
0.06
4.34
3.92
4.06
1.40
2.03
17.98
0.18
0.23
0.20
Q.ll
0.14
-
0.21
0.39
0.46
0.52
0.27
0.15
3.49
CN
0.10
-------
TABLE D-8. POINT SOURCE 3, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
7-3-79 T 6P
8P
10P
7-4-79 U 12A
2A
o
» 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL
OF FLOW/2H
0.171
0.171
0.171
0.171
0.171
0.171
0.171
0.171
0.171
NF*
NF
NF
0.171
0.000
1.539
»
Cd
0.083
0.066
0.055
0.034
0.076
0.052
0.032
0.034
0.022
-
-
-
0.050
0.021
0.65
METAL AND CYANIDE CONCENTRATIONS
(rag/D
Cr Nl . Pb Zn Cu
0.010
0.008
0.009
0.009
0.007
0.008
0.005
0.013
0.009
-
-
-
0.009
0.002
0.12
0.09
0.06
0.05
0.04
0.06
0.05
0.03
0.04
0.03
-
-
-
0.05
0.02
0.64
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.01
-
-
-
<0.01
0.00
<0.13
5.96
1.11
3.50
3.47
3.45
2.65
3.44
2.53
4.83
-
-
-
3.44
1.38
44.12
0.59
0.49
0.42
0.26
0.55
0.40
0.21
0.33
0.26
-
-
-
0.39
0.14
5.01
CN
0.14
0.16
0.15
0.13
0.16
0.17
0.21
0.12
0.30
-
-
-
0.17
0.05
2.19
*NF = No flow
-------
TABLE D-9. POINT SOURCE 3. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
7-5-79 TH 8A
10A
12P
2P
4P
8 6P
8P
IOP
7-6-79 FRI 12A
2A
4A
6A
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
.162
.162
,162
.162
.162
.162
.162
.162
.162
.162
.162
.162
.162
.000
.944
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.045
.070
.062
.058
.031
.043
.055
.036
.036
.067
.032
.032
.047
.014
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.007
0.010
0.008
*
0.006
0.010
0.006
0.011
0.010
0.013
0.010
0.007
0.014
0.009
0.003
0.07
0.06
0.07
0.06
0.04
0.13
0.12
0.05
0.05
0.05
0.03
0.02
0.06
0.03
i
<0
<0
<0
<0
0
<0
<0
<0
<0
<0
<0
0
<0
0
.
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.24
.03
.07
0.39
2.02
1.19
2.40
2.05
1.26
2.04
1.42
2.62
2.14
1.88
3.24
1.89
0.75
0.36
0.56
0.49
0.36
0.19
0.23
0.33
0.21
0.21
0.42
0.19
0.18
0.31
0.13
CN~
0.10
0.66
0.33
0.20
0.12
0.68
0.28
0.23
0.24
0.13
0.10
0.23
0.28
0.20
LBS/DAY
0.75
0.15
1.01
30.60
5.04 <4.46
-------
TABLE D-10. POINT SOURCE 4 NORTH PLANT, SAMPLING DAY ONE
' - - -' '- -__.. ., ., _, . _ - . ,_ . ---i-._j. --- r _ . -- -r-M-m-.m.- .-. ._! - -.-"_ _.-----_.__.._ I .- .-.,.-. i --TI- _ _._ii.i. - _ - .... - - _. . ., _L
DAY OF
DATE WEEK TIME
5-21-79 M 6P
8P
10P
5-22-79 12A
2A
4A
g 6A
o
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.004
.004
.004
.004
.004
.004
.004
.004
.004
.004
.004
.004
.004
.000
.048
0
<0
<0
<0
<0
<0
0
0
<0
<0
<0
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cd . Cr Nl Pb Zn
.001
.001
.001
.001
.001
.001
.001
.002
.001
.001
.001
<0.001
<0
0
.002
.001
15.83
13.36
13.86
12.72
14.68
13.40
15.96
23.64
16.63
22.25
27.41
12.20
16.83
4.91
0.01
1
0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.00
<0.01
<0.01
0.01
<0.01
0.01
<0.01
0.02
0.03
0.02
0.03
0.03
0.03
<0.02
0.01
148
15
16
15
1
0
82
78
73
75
66
49
51
44
.96
.54
.83
.91
.01
.28
.03
.16
.38
.49
.36
.19
.93
.06
Cu
0.40
0.41
0.16
0.08
0.24
0.14
0.25
0.28
0.19
0.37
0.34
0.18
0.25
0.11
CN~
<0.10
<0.10
-------
TABLE D-ll. POINT SOURCE 4 NORTH PLANT, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
5-15-79 T 6P
8P
10P
5-16-79 W 12 A
2A
4A
8 , * 6A
»-»
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
MILLION GAL,
OF FLOW/2H Cd Cr NI Pb Zn
0
0
0
0
0
0
0
0
0
0
0
0
Q
0
0
,004
.004
.004
.004
.004
.004
.Q04
.004
.004
.004
.004
.004
.004
.000
.048
0
0
0
0
0
<0
<0
<0
<0
<0
<0
<0
<0
0
.002
.002
,014
.001
.001
tooi
.001
.001
.001
.001
.001
.001
.003
.004
30.68
36,34
17,47
4.05
1,04
0.66
0.70
1.59
19.01
35.56
12.37
2.16
13.39
14.20
0.01
0,02
0.26
0.01
0.01
0.01
0.04
0.01
<0.01
0.01
<0.01
0.01
<0.03
0.07
0.07
0.01
0.13
0.05
0.03
0.02
0.02
0.02
0.03
0.04
0.02
0,02
0.04
0.03
i
11
15
892
6
0
0
0
0
11
7
8
1
79
256
.83
.18
,64
.08
.79
.36
.19
.93
.71
.74
.95
.78
.85
.00
Cu
0.07
0.08
1.80
0.25
0.04
0.02
0.02
0.02
0.02
0.16
0.05
0.13
0.22
0.50
CN~
<0.10
-------
TABLE D-12. POINT SOURCE 4 NORTH PLANT. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
5-16-79 W 6P
8P
10P
5-17-79 TH 12A
2A
1*0
o
10 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0,
0.
0.
004
004
004
004
004
004
004
004
004
004
004
004
004
000
048
Cd
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Nl Pb Zn Cu
7
10
7
5
1
2
0
15
3
13
64
14
12
17
.75
.62
.40
.09
.40
.22
.57
.68
.56
.45
.94
.53
.27
.38
0
0
0
0
<0
0
<0
0
0
0
0
0
<0
0
.01
.01
.02
.01
.01
.01
.01
.01
.01
.01
.02
.01
.01
.004
0.02
0.03
0.02
0.03
0.02
0.02
0.02
0.03
0.02
0.02
0.05
0.01
0.02
0.01
6.22
5.84
4.09
0.10
0.14
1.42
0.09
3.27
2.08
1.81
1.40
7.95
2.87
2.63
0.29
0.52
0.30
0.61
0.11
0.10
0.05
0.13
0.12
0.16
0.25
0.07
0.23
0.18
CN
-------
TABLE D-13. POINT SOURCE 4 SOUTH PLANT. SAMPLING DAY ONE
j,_j - -.- . - -- -..._,_ ---.- j-..j|- - - - - r- -.- .- 1 ff _r -in .' - , -- -- ' ' - ' - " ........ i - '- '.
DAY OF
DATE WEEK TIME
5-21-79 M 6P
8P
10P
12A
2A
3 4A
*>
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0035
.0038
,0031
.0039
.0041
.0039
.0038
.0041
.0042
.0042
.0044
.0036
.0039
.0004
.0466
Cd
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
. <0
0
.001
.001
,001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
2
16
1
1
1
1
2
1
1
0
<0
18
14
6
.31
.85
.82
.72
.49
.63
.53
.46
.44
.20
.01
.24
.14
.31
li
0.03
0.10
0.06
0.02
0.04
0.04
0.04
<0.01
0.04
0.11
0.33
0.04
10.07
0.09
.'
0.03
0.10
0.06
0.02
0.04
0.04
0.04
0.01
0.04
0.11
0.33
0.04
0.07
0.07
0.03
0.05
0.05
0.03
0.03
0.02
0.03
0.03
0.04
0.05
0.43
0.04
0.08
0.11
0.03
0.16
0.02
0.02
0.01
0.01
0.07
0.01
0.01
0.01
1.45
0.11
0.16
0.41
CN~
-------
TABLE D-14. POINT SOURCE 4 SOUTH PLANT, SAMPLING DAY TWO
o
*-
DAY OF
DATE WEEK TIME
5-15-79 T 6P
8P
10P
5-16-79 W 12A
2A
4A
I
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.0039
0.0036
0.0036
0.0041
0.0043
0.0041
0.0040
0.0030
0.0030
0.0034
0.0031
0.0037
0.0037
0.0004
0.0438
Cd
0.003
0.003
0.003
0.003
0.003
0.003
0.002
0.003
0.003
0.003
0.003
<0.001
10.003
0.001
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Ni Pb Zn Cu
2.20
2.77
1.90
1.61
1.50
2.71
1.54
1.18
1.60
0.39
2.81
7.57
2.31
1.80
0.02
0.02
0.02
0.02
0.02
0.02
0.20
0.02
0.02
0.02
0.02
0.02
0.04
0.05
0.10
0.02
0.11
0.09
0.14
0.13
0.08
0.06
0.01
0.07
0.08
0.34
0.10
0.08
0.29
0.19
0.16
0.14
0.27
0.16
0.11
0.10
0.12
0.13
0.17
0.06
0.16
0.07
0.01
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.02
0.01
0.01
0.04
0.01
0.01
CN
-------
TABLE D-15. POINT SOURCE 4 SOUTH PLANT, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
5-16-79 W 6P
8P
10P
5-17-79 TH 12A
2A
ro 4A
o
01 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0038
.0036
.0037
.0039
.0037
.0040
.0038
.0037
.0042
.0036
.0036
.0036
.0038
.0001
.0452
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.001
.001
.001
.001
.001
.001
,001
.001
.001
.001
.001
.001
.001
.000
METAL
Cr
8.
0,
6.
40.
13.
30,
21.
18.
37.
34.
2.
4.
18.
14.
49
67
73
43
14
81
83
67
86
14
61
14
29
48
AND CYANIDE CONCENTRATIONS
(rag/1)
Nl Pb Zn Cu
0 , 0'2
0.02
0,01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0,01
0.01
0.01
0.004
0.08
0.07
0.09
0.11
0.11
0.05
0.08
0.08
0.04
0.06
0.06
0.19
0.09
0.04
0.08
0.09
0.09
0.19
0.07
0.07
0.07
0.05
0.06
0.07
0.07
0.07
0.08
0.04
0.03
0.01
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.02
0.02
0.01
CN~
<0.10
-------
TABLE D-16. POINT SOURCE 5, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
7-9-79 M 6P
8P
10P
7-10-79 T 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0145
.0122
.0059
.0090
.0097
.0082
.0052
.0130
.0166
.0077
.0054
.0102
.0098
.0037
.235
Cd
0
0
0
0
0
0
0
0
0
0
0
2
0
0
.638
.116
.053
.181
.096
.126
.080
.453
.163
.184
.547
.071
.392
.564
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
39
4
5
20
33
54
43
34
32
39
26
138
39
34
.47
.86
.21
.28
.26
.38
.53
.10
.95
.90
.63
.24
.40
.39
1.97
3.68
0.96
18.79
3.16
2.70
1.85
2.86
15.02
7.46
4.59
6.40
5.79
5.57
0.07
0.02
0.02
0.12
0.05
0.05
0.03
0.14
0.07
0.05
0.10
0.06
0.07
0.04
0.65
0.40
0.34
0.34
0.35
1.75
0.55
1.98
0.67
1.41
3.18
2.66
1.19
0.99
0.55
0.13
0.39
0.55
0.35
0.39
0.30
0.69
0.33
0.26
0.87
3.36
0.68
0.87
CN
0.30
0.12
1.32
1.04
<0.10
0.10
o.io
o.io
0.22
0.19
3.80
0.25
0.64
1.07
LBS/DAY
0.41
39.12 6.21 0.067 1.10 0.67 <0.45
-------
TABLE D-17. POINT SOURCE 5, SAMPLING DAY TWO
DAY OF MILLION GAL.
DATE WEEK TIME OF FLOW/2H
7-10-79 T 6P
8P
10P
7-11-79 W 12A
2A
4A
6A
Kl
g 8A
10A
12P
2P
4P
0
0
0
0
0
0
0
0
0
0
0
0
.0122
.0108
.0103
.0083
.0070
.0052
.0040
,0069
.0111
.0089
.0108
.0041
Cd
0
0
0
0
0
0
0
0
1
0
0
1
.874
.107
.069
.040
.069
.069
.076
.889
.213
.288
.149
.415
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
43
14
18
15
59
537
79
43
33
38
27
898
.25
.98
.80
.06
.22
.12
.95
.56
.11
.78
.59
.54
1.53
;,52
1.22
0.92
0.88
0.94
0.96
0.55
18,35
5.44
6.98
3.84
0.09
0.05
0.05
0.02
0.06
0.03
0.05
0.22
0.13
0.06
0.06
0.19
2.67
0.89
0.85
0.88
0.36
0.55
0.42
4.79
3.93
1.32
1.03
2.93
1.22
0.32
0.29
0.17
0.40
0.32
0.29
0.85
1.43
0.73
0.51
2.79
CN
0.35
O.I8
0.75
0.32
0.38
1."
0.39
0.28
0.52
0.39
0.56
1.87
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
0.213
0.438 151.24 3.57 0.08 1.72 0.78 0.59
0.510 276.24 5.01 0.06 1.49 0.75 0.47
0.36 79.93 3.45 0.067 1.48 0.61 0.43
-------
TABLE D-18. POINT SOURCE 5. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
7-11-79 W
7-12-79 TH
MEAN
STANDARD
MGD
6P
8P
10P
12A
2A
4A
6A
8A
10A
12P
2P
4P
DEVIATION
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0114
.0114
.0089
.0087
.0074
.0055
.0046
.0116
.0199
.0147
.0146
.0132
.0109
.004
.264
Cd
0
0
0
1
0
0
0
1
0
1
1
1
0
0
.694
.191
.140
.341
.108
.066
.109
.265
.863
.092
.189
.739
.733
.595
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
41.39
8.18
a. 12
111,48
81.29
447.29
74.15
131.02
42.72
40.58
46.59
528.39
130.10
171.97
1.92
2.76 ,
2.59
11.55
2.59
1.69
1.85
3.14
4.81
3.91
6.08
5.31
4.02
2.77
0.10
0.14
0.04
2.28
0.38
0.19
0.19
0.51
0.17
0.31
0.54
0.22
0.42
0.61
1.63
1.64
0.56
5.41
0.85
2.14
0.83
4.14
3.39
5.89
7.14
2.59
3.02
2.19
0.98
1.14
0.94
2.85
1.15
0.64
0.70
1.74
0.96
1.22
1.52
3.26
1.43
0.83
CN
1.74
9.24
8.72
4.73
1.88
4.08
0.16
4.55
0.49
6.22
0.38
0.50
3.55
3.24
LBS/DAY
0.94 130.36 4.69 0.51 3.77 1.63 3.72
-------
TABLE D-19. POINT SOURCE 6 (SOUTH). SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
4-24-79 T 6P
8P
10P
4-25-79 W 12A
2A
B 4A
to
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
032
032
032
032
032
032
032
032
032
032
032
032
032
000
384
0
0
0
0
0
0
0
0
0
0
0
0
0
0
CcJ
.003
.003
.003
.004
.003
.003
.003
.003
,003
.003
.003
.002
.003
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cr Nl Pb Zn Cu
0.035
0.052
0.037
0.065
0.038
0.042
0.070
0.061
0.041
0.033
0.020
0.010
0.092
0.018
0.14
0.15
0.16
0.16
0.11
0.13
0.20
0.12
0.13
0.10
0.10
0.05
0.13
0.04
.
0.37
0.36
0.39
0.53
0.30
0.35
0.46
0.21
0.24
0.11
0.22
0.08
0.30
0.13
280
395
342
611
347
453
459
596
247
159
118
128
345
167
.55
.09
.26
.45
.04
.74
.16
.95
.82
.25
.33
.41
.01
.40
0.03
0.02
0.28
0.22
0.11
0.13
0.15
0.14
0.16
0.16
0..18
0.09
0.14
0.07
CN~
0.23
0.23
0.25
0.26
0.40
0.35
0.28
<0.10
0.37
0.18
<0.10
0.10
0.24
0.10
LBS/DAY
0.010 0.14 0.41 0.97 1104.90 0.45 <0.76
-------
TABLE D-2Q. POINT SOURCE 6 (SOUTH), SAMPLING DAY TWO
... _ ._ ..--.-- - .--...._ --_.,..._- - u^r-.u^^.- I. -n_--.--r-i. _ 1 - - ' * .--«.----- ." '. .-..-.--..- - '- 1 i .. ~ .. .. . . . I . . "
DAY OF
DATE WEEK TIME
4-25-79 W 6P
8P
10P
4-26-79 Th 12A
2A
4A
o 6A
8A
10A
12p
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.032
.032
.032
.032
.032
.032
.032
.032
.032
.032
.032
.032
.032
.000
.384
0
0
0
0
0
0
0
<0
<0
.002
.001
.001
.001
.002
.001
.001
.001
.001
<0.001
0
0
<0
0
.001
.001
.001
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.001
0.001
0.002
0.004
0.025
0.012
0.003
0.013
0.004
0.004
0.004
0.009
0.007
0.007
o.o?.
0.06
0.04
0.05
0.13
0.08
0.04
0.09
0.04
0.03
0.02
0.07
0.06
0.03
0.06
0.05
0.03
0.03
0.12
0.08
0.02
0.03
0.05
0.04
0.02
0.07
0.05
0.03
62
61
32
27
184
175
26
39
55
62
26
33
65
55
.76
.69
.78
.50
.27
.43
.98
.41
.12
.90
.41
.13
.70
.25
0.07
0.05
0.05
0.05
0.08
0.08
0.06
0.06
0.08
0.06
0.04
0.12
0.07
0.02
CN
<0.10
-------
TABLE D-21. POINT SOURCE 6 (SOUTH). SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
4-26-79 TH 6P
8P
10P
5-4-79 FRI 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H CcJ
0
0
0
0
0
0
0
0
0
.032
.032
.032
.032
.032
.032
.032
.032
.032
0.032
0
0
0
0
0
.032
.032
.032
.000
.384
0
<0
<0
0
0
0
0
0
0
0
0
0
<0
0
.001
.001
.001
.003
.003
.003
.003
.003
.003
.003
.003
.004
.003
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cr Ni Pb Zn Cu
0.008
0.008
0.007
0.020
0.021
0.015
0.011
0.037
0.019
0.022
0.013
0.024
0.017
0.009
O':05
0.07
0.07
0.10
0.11
0.09
0.06
0.14
0.06
0.08
0.05
0.08
0.08
0.03
0.07
0.09
0.07
0.08
0.07
0.06
0.06
0.15
0.09
0.09
0.06
0.13
0.09
0.03
37.
5.
8.
55.
89.
55.
98.
98.
105.
106.
120.
114.
74.
40.
27
99
98
87
79
16
71
90
65
75
16
25
79
66
0.09
0.14
0.11
0.14
0.15
0.12
0.10
0.60
0.12
0.14
0.07
0.14
0.16
0.14
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.13
<0.10
0.10
<0.10
<0.10
0.01
LBS/DAY
<0.008 0.055 0.27 0.27 239.52 0.51 <0.33
-------
TABLE D-22. POINT SOURCE 7, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
5-21-79 M 6P
8P
10P
5-22-79 T 12A
2A
4A
N>
U 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.000
.072
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Ni Pb Zn Cu
0.025
0.020
0.023
0.264
0.302
0.265
0.289
0.022
0.020
0.014
0.011
0.027
0.11
0.13
0.2"0'
0.11
0.15
1.93
2.24
1.48
1.84
0.11
0.10
0.13
<0.01
0.11
<0.83
0.92
0.05
0.03
0.02
0.14
0.17
0.13
0.15
0.03
0.01
0.01
<0.01
0.04
<0.07
0.07
26
16
15
33
25
30
4
19
11
1
0
84
16
11
.34
.65
.90
.95
.23
.95
.74
.39
.01
.39
.45
.41
.91
.61
1.38
1.00
0.92
9.87
12.64
8.85
11.15
0.93
0.64
0.14
0.02
0.93
4.32
5.09
CN~
<0.10
<0.10
-------
TABLE D-23. POINT SOURCE 7, SAMPLING DAY TWO
, , , , -- - -
DAY OF
DATE WEEK TIME
5-23-79 W 6P
8P
10P
5-24-79 TH 12A
2A
4A
£ 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
006
006
006
006
006
006
006
006
006
006
006
006
006
000
Cd
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
.0
.001
.001
.001
.001
.001
.001
.001
,001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS .
(»g/D
Cr Nl Pb Zn Cu
0.082
0.088
0.133
0.112
0.093
0.102
0.100
0.063
0.041
0.009
0.017
0.138
0.081
0.044
0.-39
0.46
0.84
0.69
0.55
0.65
0.59
0.29
0.07
0.07
0,11
0.89
0.47
0.30
0.09
0.12
0.10
0.08
0.06
0.07
0.07
0.09
0.11
0.04
0.04
0.11
0.08
0.03
112.
124.
120.
57.
109.
117.
111.
104.
77.
71.
74.
145.
51
14
99
40
48
67
57
92
84
34
79
25
102.33
26.09
3.62
2.42
4.37
3.42
2.62
3.21
2.88
1.52
2.02
0.69
0.88
4.71
2.69
1.27
CN~
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.00
0.072
LBS/DAY
<0.001 0.045 0.26 0.045 56.49 1.46 <0.060
-------
TABLE D-24. POINT SOURCE 7. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
5-29-79 T 6P
8P
10P
5-30-79 W 12A
2A
4A
^ 6A
8A
10A
12P
2P
4P
ME AH
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.000
.072
i
Cd
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
.001
.001
.001
.001
,001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.014
0.012
0.016
0.124
0.221
0.214
0.200
0.230
0.204
0.158
0.163
0.085
0.147
0.076
0.10
0.07
0.10
0.78
0.92
0.90
0.82
0.93
0.73
0.60
0.61
0.13
0.56
0.35
0.04
0.02
0.02
0.12
0.04
0.03
0.03
0.04
0.04
0.05
0.05
0.03
0.04
0.03
199
81
84
66
85
56
46
52
46
46
22
19
73
42
.03
.25
.11
.61
.59
.13
.67
.53
.40
.18
.04
.54
.80
.19
0.98
0.44
0.59
5.33
2.46
0.02
0.01
0.02
0.01
0.01
0.01
0.01
0.82
1.59
CN~
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.00
LBS/DAY
<0.001 0.082 0.33 0.026 43.56 0.49 <0.060
-------
TABLE D-25. POINT SOURCE 8. SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
4-16-79 M 6P
8P
XOP
4-17-79 T 12A
2A
4A
10
c 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.000
0.264
»
Cd
<0.001
<0.001
<0.001
<0,001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cr Nl Pb Zn Cu
0.025
0.086
0.047
0.031
0,016
0.011
0.007
0.011
0.015
0.020
0.039
0.035
0.033
0.024
0.05-
0.12
0.07
0.05
0.02
0.01
0.01
0.01
0.02
0.03
0.07
0.06
0.03
0.02
0.03
0.06
0.05
0.03
0.02
0.02
0.01
0.01
0.02
0.03
0.05
0.05
0.03
0.02
0.12
0.29
0.02
0.01
0.01
0.01
0.02
0.02
0.01
0.01
0.02
0.05
0.04
0.08
0.15
0.25
0.20
0.19
0.15
0.18
0.18
0.20
0.18
0.13
0.81
0.40
0.25
0.19
CN~
-------
TABLE D-26. POINT SOURCE 8, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
4-17-79 T 6P
8P
10P
4-18-79 W 12A
2A
4A
e *
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL
OF FLOW/2H
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.022
0.024
0.022
0.001
0.266
ca
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.006
0.016
0.022
0.019
0.014
0.021
0.009
0.007
0.011
0.012
0.019
0.011
0.014
0.005
0.26'
0.01
0.02
0.02
0.03
0.06
0.01
<0.01
<0.01
0.01
0.03
0.01
<0.04
0.07
0.04
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.54
0.16
0.29
0.47
0.02
0.04
0.21
8.49
1.03
0.31
0.45
0.40
1.03
2.36
0.26
0.08
0.12
0.12
0. 11
0.14
0.14
0.14
0.19
0.13
0.11
0.09
0.14
0.05
CN
<0.10
-------
TABLE D-27. POINT SOURCE 8t SAMPLING DAY THREE
M
*-^»
DAY OF
DATE WEEK TIME
4-18-79 W
4-19-79
MEAN
STANDARD
MGD
6P
8P
10P
12A
2A
4A
6A
8A
10A
12P
2P
4P
DEVIATION
MILLION GAL
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.024
.024
.024
.024
.024
.024
.024
.024
.024
.024
.024
.024
.024
.000
.288
Cd
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
'0.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.014
0.010
0.007
0.013
0.008
0.005
0.004
0.006
0.007
0.018
0.011
0.008
0.009
0.004
0.0'2
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
<0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.03
0.02
0.01
0.01
0.01
0.29
0.27
0.24
0.25
0.25
0.17
0.15
0.22
0.09
0.27
0.28
6.59
0.76
1.83
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
10
13
15
13
17
11
12
17
12
16
12
02
13
04
CN~
-------
TABLE D-28. POINT SOURCE 9, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
3-19-79 M 6P
8P
10P
3-20-79 T 12A
to 2A
i ^
w . 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.000
0.335
>
Cd
0.001
<0.001
<0.001
<0.001
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.001
<0.001
<0.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni, Pb Zn Cu
0.14
0.30
0.08
0.16
0.05
0.13
0.08
0.33
0.15
0.08
0.06
0.11
0.14
0.09
0.30
0.59
6.19
0.47
0.09
0.24
0.24
0.39
18.49
0.77
7.42
0.30
2.96
5.49
0.01
0.01
0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
<0.01
0.00
0.19
0.12
0.05
0.11
0.08
0.11
0.11
0.10
0.08
0.15
0.08
0.23
0.12
0.05
0.07
0.07
0.03
0.06
0.02
0.04
0.04
0.06
0.05
0.10
0.03
0.11
0.05
0.03
CN~
0.10
<0.10
0.24
0.10
0.10
0.10
0.10
<0.10
<0.10
<0.10
0.12
0.10
<0.11
0.40
LBS/DAY
<0.003 0.39 8.25 <0.028 0.33 0.16 <0.32
-------
TABLE D-29. POINT SOURCE 9, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
3-20-79 T 6P
8P
10P
3-21-79 W 12A
to 2A
H
4A
6A
8A
10A
12P
2P
4?
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.028
.028
.028
.028
.028
.028
.028
.028
.028
.028
.028
.028
.028
.000
.335
0
<0
<0
<0
0
0
0
0
<0
<0
<0
0
<0
Cd
.001
.001
.001
.001
.002
.002
.003
.001
.001
.001
.001
.001
.002
o.ooi
METAL AND Cl
Cr Ni
0.03
0.02
0.07
0.01
0.48
0.33
0.17
0.06
0.08
0.09
0.06
0.17
0.13
0-13
13
0
13
0
13
0
0
1
0
0
0
6
4
5
.12
.33
.31
.15
.50
.35
.31
.07
.43
.83
.28
.00
.14
.29
rSNTDTO!GN
(mg/1)
Pb
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
o.oo
.Zn
0.10
0.12
0.07
0.08
0.18
0.20
0.18
0.26
0.18
0.17
0.17
0.15
0.15
0.05
ONS
Cu
0.04
0.08
0.07
0.05
0.12
0.13
0.10
0.16
0.10
0.11
0.10
0.06
0.09
0.03
CN~
-------
TABLE D-30.
DAY OF
DATE WEEK TIME
3-21-79 W 6P
8P
10P
3-22-79 TH 12A
K 2A
o 4A
6A
8A
10A
12P
2P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H Cd
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.028
0.000
0.335
0.001
<0.001
0.001
0.001
0.002
0.002
0.002
<0.001
<0.001
0.001
0.001
< 0.002
0.001
METAL AND CYANIDE CONCENTRATIONS
(fflg/D
Cr "Ml Pb Zn Cu
0.17
0.23
0.32
0.05
0.60
0.32
0.20
0.11
0.24
0.15
0.09
0.225
0.15
2.32
5.33
0.45
0.40
0.44
0.36
0.28
0.71
5.66
3.16
1.90
1.91
2.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.13
0.09
0.15
0.16
0.24
0.18
0.11
0.13
0.26
0.07
0.14
0.15
0.06
0.10
0.07
0.11
0.06
0.14
0.15
0.11
0.09
0.11
0.07
0.08
0.09
0.02
CN~
-------
TABLE D-31.
DAY OF
DATE WEEK TIME
3-20-79 T 6P
8P
10P
3-21-79 W 12A
2A
N>
*- 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0048
.0048
.0048
.0048
.0048
,0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0000
.058
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
,001
,001
.002
.001
.001
.001
.001
.001
,002
.002
.001
.001
.001
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr N^ Pb Zn Cu
0.005
0.004
0,080
.0.002
0.002
0.016
0.040
0.007
0,006
0.005
0.004
0.027
0.016
0.023
0.12
0.18
0.42
0.15
0.14
0.20
0.33
0.42
0.12
0.09
0.08
0.15
0.20
0,12
<0.01
<0.01
0.01
<0.01
0.01
0.01
0.01
0.01
0.01
<0.01
<0.01
0.01
<0.01
0.00
0.46
1.66
0.16
0.98
1.43
1.20
4.13
1.15
1.20
0.78
0.55
0.57
1.19
1:94
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.03
.05
.12
.03
.04
.06
.15
.04
.04
.04
.03
.04
.05
.04
CN~
-------
TABLE D-32. POINT SOURCE 10. SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
3-21-79 W 6P
8P
10P
3-22-79 TH 12A
N> 2A
o
M
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0048
.0000
.058
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.001
.003
.002
.001
.002
.001
.001
.001
.003
.002
.001
.001
.002
.001
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Ni' ' Pb Zn Cu
0.003
0.036
0.084
0.003
0.133
0.037
0.009
0.006
0.125
0.052
0.019
0.012
0.043
0.047
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.09
.23
.42
.17
.47
.20
.15
.17
.48
.31
.17
.15
.25
.14
<0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
10.01
0.00
0.48
3.39
4.08
1.54
3.86
1.62
1.83
2.99
6.03
2.41
1.67
1.97
2.65
1.50
0.03
0.15
0.20
0.05
0.19
0.07
0.04
0.09
0.19
0.20
0.07
0.08
0.113
0.67
CN~
-------
TABLE D-33. POINT SOURCE 11. SAMPLING PAY ONE
DAY OF
DATE WEEK TIME
6-1-79 T 6A
8A
10A
12P
2P
4P
H 6P
8P
MEAN
STANDARD DEVIATION
MILLION GAL.
OF FLOW/ 2 H
0.0056
0.0056
0.0056
0.0056
0.0056
0.0056
0.0056
0.0056
0.0056
Cd
0.013
0.015
0.017
0.003
0.007
0.025
0.015
0.009
0.013
0.007
METAL AND CYANIDE CONCENTRATIONS
(rog/1)
Cr Nl Pb Zn Cu
< i
0.016
0.029
0.018
0.001
0.010
0.036
0.020
0.020
0.019
0.011
0.01
0.04
0.01
<0.01
0.01
0.02
0.01
<0.01
<0.02
0.02
0.07
0.93
0.75
0.13
0.23
1.42
0.07
0.62
0.53
0.49
0.51
0.69
0.74
0.10
0.26
0.92
0.50
0.35 '
0.51
0.27
0.10
0.17
0.25
0.29
0.28
0.37
0.22
0.21
0.24
0.08
CN~
0.13
0.14
0.11
<0.10
0.10
<0.10
<0.10
0.10
<0.11
0.02
MGD
LBS/DAY
0.0445
0.005
0.007 <0.006
0.20
0.19
0.088 <0.041
-------
TABLE D-34. POINT SOURCE 11. SAMPLING DAY TWO
.
DAY OF
DATE WEEK TIME
5-2-79 W 6A
8A
10A
12P
2P
4P
^ 6P
* 8P
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL.
OF FLOW/ 2 H
0.0036
0.0036
0.0036
0.0036
0.0036
0.0036
0.0036
0.0036
0.0036
0.0000
0.0288
Cd
0.005
0.006
0.011
0.032
0.016
0.016
0.018
0.020
0.016
0.009
0.004
METAL AND CYANIDE CONCENTRATIONS
(rag/1 j
Cr Ni Pb Zn Cu
0.007
0.008
0.007
0.007
0.027
0.037
0.002
<0.001
£0.012
0.013
£0.003
0.02
0.02
0.01
0.01
0.02
0.04
0.03
0.04
0.024
0.012
0.006
0.40
0.60
1.12
2.70
1.94
3.02
3.46
3.48
2.09
1.26
0.50
0.19
0.26
0.27
0.66
0.45
0.51
0.68
0.52
0.44
0.19
0.11
0.15
0.17
0.17
0.46
0.36
0.36
0.42
0.34
0.30
0.12
0.073
CN
<0.10
<0.10
<0.10
<0.10
<0.10
0.10
<0.10
<0.10
<0.10
0.00
<0.024
-------
TABLE D-35. PQIMT SOURCE 11. SAMPLING DAY THREE
METAL AND CYANIDE CONCENTRATIONS
DAY OF
DATE WEEK TIME
5-24-79 TH 6A
8A
10A
12P
2P
4P
M 6P
Ni
01 8P
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL.
OF FLOW/2H
0.0050
0.0050
0.0050
0.0050
0.0050
0.0050
0.0050
0.0050
0,0050
0.0000
0.0397
Cd
0.008
0.016
0.013
0.007
0.002
0.005
0.011
0.010
0.009
0.004
0.003
Cr
0.020
0.066
0.074
0.055
0.027
0.012
0.007
0.006
0.033
0.028
0.011
Nl
0.01
0.02 ,
0.07
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.008
(mg/1)
Pb
0.68
1.07
0.96
0.52
0.34
0.60
0.54
0.49
0.65
0.25
0.22
Zn
0.56
0.55
0.56
0.49
0.57
0.58
0.29
0.43
0.50
0.10
0.17
Cu
0.40
0.47
0.58
0.45
0.34
0.39
0.18
0.20
0.38
0.13
0.13
CN
-------
TABLE D-36.
POINT SOURCE 12^ SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
2-19-79 M 6P
8P
10P
2-20-79 T 12A
2A
^ 4A
cri 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
LBS/DAY
MILLION GAL.
OF FLOW/2H Cd
0.003
0.003
0.015
0.015
0.004
0.004
0.030
0.030
0.013
0.013
0.007
0.007
0.012
0.010
0.114
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.003
<0.001
0.001
<0.001
<0.002
0.001
<0.00
1
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
2.29
0.07
5.06
5.28
1.71
0.51
0.23
1.21
0.09
0.12
2.34
0.11
1.59
1.88
1.95
t t
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.01
0.01
<0.02
0.01
,
<0.012
0.06
0.06
0.05
0.03
0.02
0.02
0.01
0.06
0.03
0.01
0.04
0.04
0.04
0.02
0.041
0.064
0.051
0.060
0.074
0.047
0.051
0.046
0.055
0.052
0.047
0.141
0.040
0.061
0.027
0.069
3.96
1.09
2.73
1.32
0.96
0.77
0.72
1.71
10.75
0.97
5.17
0.60
2.56
2.95
2.91
CN
<0. 10
<0.10
<0.10
-------
TABLE D-37. POINT SOURCE 12. SAMPLING DAY TOO
DAY OF
DATE WEEK TIME
2-13-79 T 6P
8P
10P
2-14-79 W 12A
2A
4A
Isl
*J 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.011
.011
.015
.015
.021
.021
.027
.027
.014
.014
.014
.014
.017
.006
.204
*
Cd
0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
-------
TABLE D-38. POINT SOURCE 12, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
2-14-79 W 6P
8P
10P
2-15-79 TH 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
012
012
010
013
013
039
039
013
013
013
014
014
018
010
205
Cd
0,002
<0,001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.001
0.001
<0.001
<0.001
<0.002
0.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.92
0.88
0.69
13.48
2.15
0.16
0.10
0.11
0.41
2.14
1.14
25.23
3.95
7.65
-------
APPENDIX £
TRUNKLINE MONITORING TABLES
TABLE 5-1. CLASSIFICATION AND CODE OF SIX MAJOR TRUNKLINES TO THE
KOKOMO POTW
Trunkline
Code
Classification
Dixon Road T-1
Fayble T-2
New Pete's Run " T-3
Northside T-4
North West T-6
Pete's Hun T-5
North Northside Int. T-4a
Indiana Feeder 7-4a-1
Washington Feeder T-4a-2
Apperson Feeder T-4a-3
South Northside Int. T-4b
Union Feeder T-4b-1
Old Park Road T-5b
Residential
Residential
Residential, Commercial, and Industrial
Residential, Commercial, and Industrial
Residential
Residential, Commercial, and Industrial
229
-------
TABLE E-2. DIXON ROAD INTERCEPTOR TRUNKLINE, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
4-24-78 M 6P
8P
10P
4-25-78 T 12A
2A
£ 4A
0
5-2-78 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.025
.028
.026
.024
.029
.030
.020
.025
.029
.050
.048
.046
.032
.010
.380
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
Cd
,001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.007
0.006
0.011
0.006
0.008
0.022
0.003
0.001
0.002
0.008
0.006
0.002
0.007
0.006
I i
<0.01
<0.01
0.01
0.01
<0.01
0.01
0.01
0.01
0.01
0.01
0.01
<0.01
<0.01
0.00
0.01
0.01
0.01
0.02
0.03
0.06
<0.01
<0.01
0.01
0.02
0.02
<0.01
<0.02
0.02
0.062
0.053
0.080
0.080
0.132
0.251
0.032
0.078
0.223
0.083
0.085
0.025
0.098
0.070
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
o'.
0.
0.
055
060
080
069
043
076
020
025
051
033
051
019
049
021
CN
-------
TABLE E-3. DIXQN ROAD INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
4-11-78 T 6P
8P
10P
4-12-78 W 12A
2A
; AA
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.045
.046
.043
.039
.036
.035
.036
.039
.040
.040
.040
.039
.040
.003
.478
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
Cd
.001
.001
,001
.001
.001
.001
.001
.001
.001
,001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cr Nl Pb Zn Cu
0.001
0.003
0.003
0.004
0.001
0.003
0.001
0.001
0.002
0.003
0,002
0.003
0.002
0.001
-------
TABLE E-4. DIXON ROAD INTERCEPTOR TRUNKLINE. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
4-12-78 W 6P
8P
10P
4-13-78 TH 12A
2A
to 4A
u>
10 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.039
.039
.037
.033
.031
.030
.030
.034
.034
.033
.033
.033
.034
.003
.406
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
Cd
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.003
0.006
0.006
0.005
0.005
0.003
0.003
0.002
0.001
0.004
0.008
0.005
0.004
0.002
O.O'l
0.01
0.01
0.01
0.01
0.01
0.01
0.01
<0.01
<0.01
0.01
0.01
<0.01
0.00
0.01
0.01
0.02
0.01
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.00
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.049
.063
.079
.061
.048
.048
.034
.034
.023
.064
.025
.053
.048
.017
0.059
0.058
0.059
0.036
0.027
0.023
0.016
0.026
0.026
0.069
0.021
0.066
0.041
0.020
CN
-------
TABLE E-5. FAYBLE INTERCEPTOR TRUNKLINE. SAMPLING DAY ONE
" "" - ' -' 1. ... I .... I.,.,. _..,.. M. I ...l| . , __ ... ..ft -. - . mi. -- - .._.._n " - _ -. - - J. - IT,. ..-.-,.- .. J - -L. .- . -1L- , 1 .__- -__..L r- -:..r+. ..---.._,--- |_- -
DAY OF
DATE WEEK TIME
1-22-79 M 6P
8P
10P
1-23-79 T 12A
2A
j 4A
j
J 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
.027
.027
.025
.019
.014
.011
.014
0.027
0
0
0
0
0
0
0
.028
.027
.027
.027
.023
.006
.273
<0
<0
<0
<0
0
0
<0
<0
<0
<0
<0
0
<0
0
Cd
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.020
0.017
0.010
0.003
0.015
<0.001
<0.001
<0.001
<0.001
0.009
0.007
0.001
<0.010
0.001
olbi
0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
0.02
<0.01
0.00
<0
<0
<0
0
0
0
0
<0
<0
<0
<0
<0
<0
0
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.00
0.14
0.14
0.14
0.27
0.16
0.13
0.08
0.07
0.12
0.17
0.16
0.34
0.16
0.08
0.12
0.12
0.14
0.10
0.10
0.10
0.08
0.07
0.12
0.18
0.14
0.31
0.13
0.06
CN
<0.10
<0.10
-------
TABLE E-6. FAYBLE INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
6-25-79 M 6P
8P
10P
6-26-79 T 12A
2A
4A
NJ
LJ
* 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.059
0.061
0.057
0.055
0.043
0.036
0.034
0.046
0.066
0.085
0.062
0.057
0.055
0.014
0.661
0.001
0.001
0.001
0.002
0.001
0.003
0.003
0.003
0.004
0.001
<0.001
0.003
10.002
0.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.017
0.014
0.008
0.013
0.010
0.020
0.017
0.014
0.015
0.025
0.010
0.012
0.015
0.005
oioi
0.01
0.01
<0.01
0.01
0.02
0.01
0.01
0.01
0.01
<0.01
0.02
<0.01
0.00
0.03
0.03
0.02
0.02
0.02
0.02
0.04
0.03
0.03
0.02
0.04
0.03
0.03
0.01
0.05
0.04
0.04
0.03
0.04
0.03
0.03
0.02
0.03
0.28
0.17
0.03
0.07
0.08
0.23
0.23
0.19
0.17
0.18
0.14
0.14
0.11
0.14
0.34
0.25
0.16
0.19
0.06
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
-------
TABLE E-7. FAYBLE INTERCEPTOR TRUNKLINE. SAMPLING DAY THREE
- -- - - - i . - T .in. - _-- j - .- . -- - - ..-..-._ .......__ _ _ . . . ... . .,,, i i.i 1.1... i
DAY OF
DATE WEEK TIME
6-26-79 T 6P
8P
10P
6-27-79 W 12A
2A
4A
fn 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.063
0.098
0.085
0.045
0.041
0.035
0.036
0.048
0.067
0.063
0.079
0.071
0.061
0.020
0.731
Cd
0.005
0.004
0.003
0.003
0.003
0.003
0.007
0.004
0,002
0.002
0.001
0.001
0.003
0.002
METAL
Cr
0.214
0.065
0.039
0.030
0.016
0.018
0.036
0.023
0.027
0.015
0.013
0.021
0.043
0.056
AND CYANIDE CONCENTRATIONS
(mg/1)
Nl Pb Zn Cu
0'.09
0.02
0.02
0.01
0.01
0.01
0.11
0.01
0.01
<0.01
0.01
0.02
<0.03
0.04
0.11
0.11
0.07
0.08
0.03
0.03
0.06
0.04
0.04
0.04
0.03
0.04
0.06
0.03
5.26
5.87
4.18
4.04
0.39
0.26
6.43
0.42
3.78
1.08
0.24
0.31
2.69
2.46
0.62
0.53
0.40
0.37
0.16
0.15
0.39
0.17
0.27
0.16
0.17
0.22
0.30
0.16
CN~
<0.10
<0.10
0.23
<0.10
<0.10
0.88
0.26
1.32
0.20
0.11
-------
TABLE E-8. FAYBLE INTERCEPTOR TRUNKLINE. SAMPLING DAY FOUR
1-.-.-- .I_.J_- r J_ T ~. - L 'I _ _^ ' ' - -.." _.. ..-..- l-t.f ...-.J- " - -' "- -' ' ' ' ' ' " .. .«-' . !-.... . '" - -" ' ' - J-MH. - ..' - . - ! 1 1 "1 -"
DAY OF
DATE WEEK TIME
6-27-79 W 6P
8P
10P
6-28-79 TH 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.082
0.107
0.092
0.067
0.052
0.044
0.046
0.060
0.077
0.076
0.085
0.079
0.072
0.019
0.867
0.001
0.001
0.001
0.001
0.001
0.001
<0.001
0.001
0.001
0.001
0.001
0.001
10.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(rog/1)
Cr Ni Pb Zn Cu
0.087
0.017
0.016
0.014
0.013
0.020
0.007
0.006
0.018
0.013
0.012
0.006
0.019
0.022
'0.01
0.01
0.01
0.01
<0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
10.01
o.oi
0.04
0.04
0.03
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.01
0.54
0.62
0.61
0.31
0.29
0.30
0.35
0.29
0.26
0.38
0.95
0.27
0.43
0.21
0.19
0.22
0.19
0.13
0.15
0.13
0.13
0.10
0.15
0.16
0.18
0.15
0.16
0.03
CN~
-------
TABLE E-9. NEW PETE'S RUN TRUNKLINE. SAMPLING DAY ONE
1 -"'-"" - ' - '- -- « -r 1__- ._- - r :.- . ji .. - _. .---- -.- -u n-_j -_ _ _ --- --L -JJ^_... .. .._.^..i.n- -...-. i . _.L-I-.L- --
DAY OF
DATE WEEK TIME
9-25-78 M 6P
8P
10P
9-26-78 T 12A
2A
xi
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
.298
.295
.283
.253
.231
.238
.246
.291
.257
.160
.207
.298
.255
.042
.057
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.18
.12
.12
.19
.13
.13
.12
.09
.14
.21
.21
.11
.15
.04
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.010
0.022
0.008
0.004
0.004
0.009
0.008
0.006
0.006
0.008
0.007
0.007
0,008
0.004
t ,
0.22
0.21
0.19
0.18
0.16
0.19
0.17
0.14
0.14
0.05
0.02
0.13
0.15
0.06
0.01
0.01
0.02
0.01
0.01
0.02
0.01
0.01
0.01
0.03
0.02
0.01
0.014
0.006
0.44
0.62
0.65
0.48
0.33
0.42
0.36
0.33
0.77
0.94
0.92
0.68
0.58
0.22
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
82
69
55
69
60
78
58
53
73
35
22
69
60
17
CN
0.21
0.39
0.46
0.67
0.49
0.52
0.42
0.37
0.29
<0,10
<0.10
0.23
<0.10
0.20
LBS/DAY
3.62 0.22 3.99 0.33 14.47 15.82 <8.91
-------
TABLE E-10. NEW PETE'S RUN TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
9-26-78 T 6P
8P
10p
9-27-78 W 12A
2A
B 4A
oo
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
.275
.268
.231
.224
.148
.093
.104
.148
.246
.302
.298
.291
.219
.076
.628
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.19
.01
.14
.11
.12
.06
.01
.07
.10
.18
.32
.18
.12
.09
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.017
0.006
0.009
0.008
0.007
0.004
0.007
0.008
0.053
0.278
0.022
0.007
0.036
0.077
0
0
0
0
0
0
0
0
0
0
0
0
0
0
i (
.15
.01
.10
.12
.15
.07
.04
.04
.01
.34
.30
.14
.12
.11
0.02
0.01
0.01
0.02
0.01
0.02
0.02
0.02
0.01
0.02
0.02
0.01
0.02
0.01
0.59
0.06
0.24
0.54
0.23
0.33
0.30
0.67
0.58
0.38
0.67
0.23
0.40
0.21
0.65
0.06
0.33
0.41
0.45
0.29
0.07
0.08
0.24
0.51
0.87
0.49
0.37
0.25
CN
0.62
0.32
0.17
0.25
0.56
o.io
-------
TABLE E-ll. NEW PETE'S RUM TRUNKLINE, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
9-27-78 W 6P
8P
10P
9-28-78 Th 12A
2A
4A
>x> 6A
8A
10A
12P
2P
4?
MEAN
STANDARD DEVIATION
MGD
_ - - - --- T -- n
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
257
203
143
130
115
0.101
0.093
0.
0.
0.
0.
0.
0.
0.
2.
170
221
268
298
287
191
075
286
Cd
0.
0.
0.
0.
0.
0.
0.
0.
0.
0,
0.
0.
0.
0.
14.
23
12
26
18
03
03
04
14
12
11
18
13
07
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Nt Pb Zn Cu
0.264
0.275
0.060
0.031
0.003
0.002
0.322
0.073
0,233
0.233
0.015
0.006
0.13
0.13
0.37
0.41
0.07
0.09
0.03
0.03
0.20
0.01
0.27
0.23
0.14
0.15
0.17
0.13
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.01
.01
.02
.03
.01
.01
.02
.02
.01
.01
.01
.01
.015
.007
0.36
0.31
0.31
0.71
0.21
0.14
0.25
0.30
0.39
0.36
0.32
0129
0.33
0.14
0.57
0.60
0.14
0.18
0.08
0.09
0.36
0.43
0.60
0.59
0.53
0.70
0.41
0.23
CN~
0.29
0.14
<0.10
<0.10
<0.10
<0.10
0.10
0.13
0.69
0.24
0.10
0.11
<0.18
0.17
LBS/DAY
2.62 2.52 3.61 0.26 6.38 9.06 <3.85
-------
SAMPLING DAY ONE
o
TABLE E 12. NORTH NORTHbiUE imtK^&i'iuK. ituiMKi^nc., anm m. ^ -
DAY OF
DATE WEEK TIME
6-12-78 M 6P
8P
10P
6-13-78 T 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
.350
.334
.323
.311
.291
.271
.258
.265
.312
.347
.353
.344
.313
.035
.760
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.22
.12
.15
.20
.14
.18
.22
.23
.16
.16
.07
.09
.16
.05
METAL AND CYANIDE CONCENTRATIONS
(fflg/D
Cr Nl Pb Zn Cu
1,07
1.15
1.09
1.53
0.77
1.70
1.54
0.49
0.69
1.06
1.00
0.80
1.07
0.37
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
17
14
20
24
06
17
08
07
08
38
20
23
17
09
0.02
0.04
0.04
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.03
0.03
0.02
0.01
1.96
2.96
0.79
0.74
0.66
0.72
0.82
1.34
1.79
3.42
2.60
3.17
1.75
1.06
0.10
0.09
0.09
0.12
0.08
0.08
0.08
0.08
0.13
0.12
0.10
0.11
0.10
0.02
CN
<0.10
<0.10
0.18
0.10
<0.10
<0.10
<0.10
0.10
<0.10
<0.10
<0.10
<0.10
<0.11
0.02
LBS/DAY
4.97 33.44 5.48 0.65 57.27 3.14 <3.35
-------
TABLE E-13. NORTH NORTHSIDE INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
6-6-78 T 6P
8P
10P
6-7-78 W 12A
2A
M 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6
.340
.338
.338
.315
.290
.664
.803
.803
.775
.614
.473
.426
.515
.204
.179
Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
,13
,07
,07
.05
.06
.48
.14
.03
.01
.02
.04
.01
.09
.13
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
1.14
1.05
0.77
0.78
1.06
1.56
0.63
1.11
0.87
1.17
0.81
0.77
0.98
0.26
i i
0.14
0.17
0.15
0.15
0.12
0.18
0.05
0.04
0.08
0.08
0.14
0.13
0.12
0.05
0.04
0.06
0.02
0.02
0.02
0.30
0.11
0.09
0.07
0.05
0.06
0.05
0.07
0.08
1
1
1
1
1
3
1
0
1
0
1
1
1
0
.22
.64
.46
.44
.49
.91
.29
.60
.10
.92
.76
.27
.51
.82
0.11
0.10
0.08
0.08
0.10
0.48
0.11
0.09
0.08
0.07
0.13
0.07
0.13
0.11
CN~
<0.10
0.10
0.10
0.10
0.10
0.22
<0.10
<0.10
<0.10
<0.10
0.10
0.10
-------
TABLE E-14. NORTH NORTHSIDE INTERCEPTOR TRUMKLINE, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
6-7-78 W 6P
8P
10P
6-8-78 TH 12A
2A
K> 4A
£ 6A
8A
IDA
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.375
0.388
0.369
0.351
0.331
0.283
0.298
0.313
0.352
0.366
0.293
0.274
0.333
0.039
3.993
Cd
0.04
0.06
0.07
0.12
0.04
0.03
0.09
0.09
0.08
0.09
0.03
0.02
0.06
0.03
METAL AND CYANIDE CONCENTRATIONS
(mg/D
Cr Ni Pb Zn Cu
0.68
1.33
1.54
0.61
0.88
0.60
1.30
0.62
0.99
0.78
0.47
0.84
0.89
0.34
0.13
0.16
0.09
0.07
0.13
0.07
0.05
0.10
0.08
0.15
0.11
0.15
0.11
0.04
0.05
0.05
0.02
0.01
0.01
<0.01
<0.01
<0.01
0.01
0.04
0.02
0.03
10.02
0.02
1.20
1.15
1.21
1.06
1.66
1.32
1.03
1.64
1.72
1.31
1.58
1.61
1.37
0.25
0.09
0.08
0.07
0.07
0.08
0.06
0.06
0.06
0.07
0.10
0.08
0.08
0.08
0.01
CN
<0.10
0.10
0.10
0.10
0.10
<0.10
<0.10
<0.10
<0.10
<0.10 .
0.10
<0.10
<0.10
0.00
LBS/DAY
2.15 30.00 3.62 <0.78
45.42 2.52 <3.33
-------
TABLE E-15. NORTHWEST INTERCEPTOR TRUNKLINE, SAMPLING DAY ONE
LO
DAY OF
DATE WEEK TIME
5-1-78 M 6P
8P
10P
5-2-78 T 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
015
014
014
Oil
009
009
010
014
014
013
012
013
012
002
148
Cd
0
Q
<0
<0
<0
-------
TABLE E-16. NORTHWEST INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
4-11-78 T 6P
8P
10P
4-12-78 W 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.010
.008
.008
.008
.008
.007
.007
.006
.006
.006
.006
.006
.007
.001
.086
*
Cd
0
<0
<0
<0
0
<0
<0
<0
<0
<0
<0
<0
<0
0
.002
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.002
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.001
0.002
0.001
<0.001
0.002
<0.001
<0.001
<0.001
<0.001
0.001
<0.001
0.001
< 0.002
0.001
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.00
<0.01
0.01
<0.01
<0.01
0.02
<0.01
0.02
<0.01
<0.01
<0.01
0.01
0.01
<0.02
0.01
0.090
0.066
0.073
0.053
0.068
0.059
0.061
0.044
0.059
0.055
0.037
0.054
0.061
0.014
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
012
010
007
.006
005
004
005
003
Oil
013
009
014
008
004
CN~
<0.10
<0.10
-------
TABLE E-17. NORTHWEST INTERCEPTOR TRUNKLINE. SAMPLING DAY THREE
., . . , .,,_. i... . , - ..,. . -'-.!,. .1.1 ... .- «. -,.-.,,!,, . ... ... Lg _-..._,..... . ... __ .. ..... r _ i,. , - -- ~ ..-- - ..... . _ __u_rn ----.-- - ' -- ' " ---
DAY OF
DATE WEEK TIME
4-12-78 W 6P
8P
10P
4-13-78 TH 12A
i 2A
g
ui 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
.006
.006
.005
.005
.005
.005
.005
.005
.005
.005
.004
.005
.005
0.001
0
.061
<0
<0
0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
Cd
.001
.001
,001
.001
,001
.001
,001
,001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(n*g/D
Cr Nl Pb Zn Cu
0
0
0
.0
0
0
0
0
<0
0
0
0
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
10.001
0
.000
-------
TABLE E-18. SOUTH NORTHSIDE INTERCEPTOR TRUNKLINE, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
6-5-78 M 6P
8P
10P
6-6-78 T 12A
2A
N, 4A
** 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.074
.075
.072
.066
.058
.056
.059
.079
.076
.082
.083
.074
.071
.009
.854
0
0
<0
<0
<0
<0
<0
0
0
<0
0
0
<0
Cd
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.003
.001
.002
o.ooi
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Nl Pb Zn Cu
0.370
0.053
0.084
0.036
0.016
0.012
0.020
0.020
0.009
0.007
0.011
0.048
0.057
0.101
t ,
0.02
0.01
0.02
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.02
0.01
0.11
0.02
0.01
0.01
<0.01
<0.01
0.01
<0.01
0.01
<0.01
0.01
0.01
10.02
0.03
0.26
0.33
0.30
0.25
0.23
0.23
0.48
0.28
0.34
0.49
0.23
0.35
0.31
0.09
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
10
10
11
09
08
05
17
07
98
09
10
61
30
49
CN
<0.10
-------
TABLE E-19. SOUTH NORTHSIDE INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
6-13-78 T 6P
8P
10P
6-14-78 W 12A
2A
£ 4A
6A
8A
10A
12P
2P
6-7-78 4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.076
.076
.072
.064
.062
.064
.072
.087
.088
.088
.075
.079
.075
.009
.903
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
<0
0
Cd
.001
.001
,001
.001
.001
.001
,001
.001
.001
.001
.001
.001
.001
.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.040
' 0.008
0.019
0.035
0.011
0.023
0.016
0.012
0.040
0.016
0.024
0.035
0.023
0.012
0.02
<0.01
<0.01
0.02
0.01
0.02
<0.01
<0.01
<0.01
0.02
0.02
0.02
<0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.01
0.00
1.
1.
1.
1.
1.
1.
1.
2.
1.
1.
2.
0.
1.
0.
31
84
59
50
67
58
85
20
58
49
02
35
58
46
0.10
0.07
0.07
0.10
0.06
0.05
0.05
0.07
0.07
0.36
0.48
0.09
0.13
0.14
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
-------
TABLE E-20. SOUTH NORTHSIDE INTERCEPTOR TRUNKLINE, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
6-7-78 W 6P
8P
10P
6-8-78 TH 12A
2A
£ 4A
Oo
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
079
077
074
068
062
059
060
070
070
041
093
076
069
013
829
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.003
.002
,002
.001
.002
.001
.002
.001
.001
.001
.001
,001
.002
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.021
0.017
0.016
0.011
0.012
0.018
0.017
0.024
0.019
0.013
0.035
0.036
0.02
0.01
11
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
0.02
<0.02
0.01
0.02
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.03
0.01
0.02
0.03
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.31
.19
.18
.14
.19
.31
.40
.37
.37
.43
.52
.66
.34
.15
0.09
0.08
0.08
0.06
0.06
0.09
0.08
0.06
0.07
0.07
0.20
0.07
0.08
0.04
CN~
-------
TABLE E-21. APPERSONWAY FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
7-17-78 M 6P
8P
10P
7-18-78 T 12A
2A
s,
b 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.081
.080
.078
.075
.069
,061
.059
,061
.067
.074
.079
.080
.072
.008
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.003
.003
,001
.001
.001
.003
.002
.002
.003
.006
.003
.002
.003
.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn
0.003
0.017
0.004
0.004
0,003
0.007
0.008
0.004
<0.001
0.006
0.003
0.011
< 0.003
0.002
O."l9
0.07
0.02
0.03
0.02
0.02
0.01
0.03
0.25
0.17
0.18
0.26
0.10
0.10
0.02
0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.02
0.06
0.03
<0.02
0.02
0.56
0.13
0.12
0.09
0.14
0.09
0.04
0.05
0.43
0.43
0.71
1.06
0.32
0.32
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cu
.052
.055
.040
.036
.029
.016
.005
.009
.015
.030
.054
.090
.040
.024
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
-------
TABLE E-22. APPERSQNWAY FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
7-19-78 W 6P
8P
10P
7-20-78 TH 12A
2A
4A
f\
D 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.081
.080
.076
.071
.063
.055
.052
.060
.067
.079
.086
.082
.071
.011
.852
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cd
.004
.002
.002
.002
.001
.001
.003
.002
.043
.003
.001
.002
.006
.012
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn
0.008
0.007
0,004
0.006
0.010
0.010
0.010
0.007
1.170
0.012
0.010
0.011
0.105
0.335
0.'21
0.06
0.01
0.03
0.02
0.02
0.02
0.01
0.12
0.14
0.11
0.34
0.09
0.10
0.03
0.02
0.01
0.01
0.01
0.01
0.01
<0.01
<0.01
0.02
0.03
0.02
<0.02
0.01
0.39
0.13
0.14
0.12
0.04
0.80
0.09
0.06
0.93
0.38
1.18
1.17
0.45
0.44
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cu
.058
.042
.028
.036
.023
.015
.021
.007
.401
.053
.037
.088
.066
.110
CN
-------
TABLE E-23. APPERSONWAY FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
7-24-78 M 6P
8P
10P
7-25-78 T 12A
2A
^ 4A
Oi
H 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
074
070
070
063
055
053
056
063
072
077
076
074
067
009
803
Cd
0.005
0.013
<0.001
0,031
<0.001
0.002
<0.001
<0.001
0.001
<0.001
<0.001
0.001
<0.009
0.009
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Nl Pb Zn
0,016
0.016
0.006
0.009
0.008
0.005
0.008
0.003
0,005
0.008
0.010
0.021
0.010
0.005
0'.09
0.05
0.02
0.03
0.01
0.01
0.01
0.01
0.13
0.16
0.20
0.35
0.09
0.11
0.02
0.02
0.01
0.06
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.02
0.02
21.
44.
0.
114.
0.
20.
0.
0.
0.
0.
0.
0.
16.
33.
52
52
26
86
22
25
16
14
13
32
87
70
99
82
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cu
.038
.051
.061
.027
.017
.018
.016
.017
.015
.027
.028
.081
.033
.021
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.00
LBS/DAY
<0.032 0.15 0.65 <0.l] 110.24 0.23 <0.67
-------
TABLE E-24. INDIANA STREET FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR, SAMPLING DAY ONE
Cn
DAY OF
DATE WEEK TIME
7-24-78 M 6P
8P
10P
7-25-78 T 12A
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL
OF FLOW/ 211
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
021
020
019
016
012
Oil
012
017
020
020
020
020
017
004
208
Cd
0
0
0
0
<0
<0
0
0
0
0
0
<0
<0
0
.019
.002
,005
.002
.001
.001
.004
.002
.001
.001
.003
.001
.004
.006
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn
0.245
0.281
0.002
<0,001
0.002
<0.001
<0.001
0.002
0.002
<0.001
<0.001
0.002
<0.045
0.102
0.01
0.02
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.02
0.01
0.01
0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
.0.00
2.01
7.35
14.83
0.23
0.86
0.15
12.69
0.11
0.13
0.22
0.13
0.14
3.24
5.34
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cu
.055
.062
.050
.056
.038
.044
.018
.033
.039
.050
.047
.046
.045
.012
CN
-------
TABLE E-25. INDIANA STREET FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR. SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
7-26-78 W 6P
8P
10P
7-27-78 Th 12A
2A
tn
01 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.020
.020
.021
.018
.013
.011
.014
.019
.021
.022
.021
.020
.018
.004
.220
<0
0
<0
0
0
<0
0
0
<0
<0
<0
<0
<0
0
Cd
,001
.002
,001
,002
,001
.001
,001
.001
.001
,001
.001
.001
.002
.001
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Ni Pb Zn Cu
<0
0
0
0
<0
0
0
0
<0
0
<0
<0
-------
TABLE E-26. INDIANA STREET FEEDER LINE TO THE NORTH NQRTHSIDE INTERCEPTOR, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
8-1-78 T 6P
8P
10P
8-2-78 W 12A
2A
Cn
*- 4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL,
OF FLOW/2H Cd
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.019
.017
.017
.013
.009
.008
.013
.050
.069
.055
.023
.021
.026
.020
.314
0.001
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.001
<0.001
0.000
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni- Pb Zn
0.001
0.001
<0.001
0.001
0.051
0.068
0.220
0.056
0.057
0.063
0.076
0.023
0.056
0.061
<0.01
0.03
<0.01
0.01
0.03
0.04
0.12
0.04
0.03
0.04
0.04
0.03
10.04
0.03
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.03
0.04
0.01
0.01
0.01
<0.02
0.01
0
0
0
0
0
0
0
1
1
0
1
1
0
0
.79
.81
.87
.85
.58
.44
.98
.93
.46
.89
.01
.12
.98
.40
0
0
0
0
0
b
5
11
10
0
36
0
5
10
Cu
.044
.051
.061
.052
.035
.118
.772
.980
.002
.025
.999
.049
.441
.832
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.00
LBS/DAY
<0.002 <0.13 <0.091 <0.052 3.38 18.53 <0.26
-------
TABLE E-27. WASHINGTON STREET FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
6-26-78 M 6P
8P
10P
6-27-78 T 12A
2A
4A
!" AA
Cn 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
.143
.133
.130
.123
.112
.108
.109
.119
.140
.146
.145
.145
.129
.015
.553
Cd
0,
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
10
18
06
07
05
05
05
04
38
38
44
14
16
15
3
1
1
2
2
1
1
4
4
4
1
2
2
1
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
.05
.68
.67
.23
.83
.63
.96
.10
.68
.69
.88
.35
.73
.16
0.17
0.21
0.14
0.17
0.15
0.13
0.05
0.07
0.24
0.15
0.11
0.09
0.14
0.06
0.02
0.02
0.01
0.01
0..01
0.01
<0.01
0.01
0.01
0.02
0.07
0.01
<0.02
0.02
3.54
2.41
2.49
2.75
2.80
2.22
2.15
2.87
1.78
1.78
48.34
2.79
6.33
13.34
0.45
0.34
0.30
0.31
0.22
0.28
0.13
0.20
0.16
0.21
0.20
0.15
0.25
0.09
CN~
0.72
o.io
-------
TABLE E-28. WASHINGTON STREET FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR, SAMPLING PAY TWO
DAY OF
DATE WEEK TIME
6-27-78 T 6P
8p
lOp
6-28-78 W 12A
2A
t^*i A A
^j\ ^^
Ov
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.138
0.130
0.127
0.120
0.112
0.106
0.107
0.118
0.140
0.148
0.183
0.146
0.131
0.022
1.575
Cd
0.09
0.04
0.03
0.03
0.03
0.02
0.02
0.05
0.30
0.48
0.10
0.11
0.11
0.14
METAL AND
Cr Nl
5.93
5.58
5.40
5.83
2.38
1.76
1.03
0.84
3.97
2.20
0.58
0.47
3.00
2.20
0.27
0.18
0.18
0.16
0.20
0.14
0.14
0.14
0.20
0.26
0.22
0.24
0.19
0.05
CYANIDE CONCENTRATIONS
(rag/1)
Pb Zn Cu
0.02
0.02
0.01
0.02
0.02
0.01
0.01
0.01
0.01
0.02
0.01
0.02
0.02
0.01
1.92
9.44
2.02
2.01
2.38
1.86
2.80
1.07
1.70
1.16
0.95
0.75
2.34
2.32
0.23
0.44
0.16
0.18
0.22
0.18
0.16
0.20
0.13
0.24
0.14
0.15
0.20
0.08
CN~
<0.10
0.10
0.10
0.10
0.12
o.io
o.io
o.io
o.io
o.io
-------
TABLE E-29. WASHINGTON STREET FEEDER LINE TO THE NORTH NORTHSIDE INTERCEPTOR. SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
6-28-78 W 6P
6-21-78 8P
10P
6-29-78 TH 12A
2A
Ui
^ 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.143
0.138
0.134
0.128
0.122
0.113
0.111
0.125
0.157
0.159
0.163
0.153
0.137
0.018
1.648
cd
0,11
0.35
0.10
0.01
0.14
0.47
0.20
0.38
0.12
0.36
0.10
0.06
0.20
0.15
METAL AND
Cr Ni
2.55
4.21
5.31
1.36
1.59
3.54
1.65
0.81
1.24
1.51
0.85
0.66
2.11
1.49
0.44
1.03
0.21
0.13
0.19
0,11
0.07
0.07
0.75
0.28
0.17
0.19
0.30
0.30
CYANIDE CONCENTRATIONS
Pb Zn Cu
0.02
O.OZ
0.01
0.01
0.02
0.01
0.03
0.02
0.03
0.03
0.05
0.03
0.02
0.01
3.40
7.38
3.35
1.40
2.53
3.24
2.66
2.13
2.06
2.16
2.08
1.70
2.84
1.57
0.27
3.71
0.54
0.10
.0.59
3.84
0.18
0.18
0.16
0.25
0.28
1.77
0.99
1.38
CN
0.10
0.44
9.33
0.49
0.69
1.39
0.21
0.32
0.51
0.46
0.41
0.18
1.21
2.58
LBS/DAY
2.68 28.22 4.32 0.33 38.66 13.05 16.18
-------
TABLE E-3Q. UNION STREET FEEDER LINE TO THE SOUTH NQRTHSIDE INTERCEPTOR, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
8-14-78 M 6P
8P
10P
8-15-78 T 12A
2A
K 4A
6A
8A
10A
12P
2P
8-22-78 4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.050
0.049
0.048
0.044
0.044
0.046
0.050
0.053
0.055
0.048
0.047
0.042
0.048
0.004
0.576
<0.001
<0.001
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.001
<0.001
<0.001
<0.001
0.000
METAL
Cr
0.187
0.083
0.147
0.160
0.148
0.065
0.136
0.084
0.173
1 0.157
0.130
0.141
0.134
0.038
AND CYANIDE CONCENTRATIONS
(mg/1)
Nl Pb Zn Cu
0.02
0.04
0.04
0.03
0.04
0.03
0.04
0.04
0.05
0.04
0.06
0.06
0.04
0.01
0.02
<0.01
0.01
0.01
<0.01
<0.01
0.03
<0.01
0.01
0.03
0.02
0.02
<0.02
0.01
3.75
2.13
2.08
1.53
1.54
0.88
2.71
1.88
2.11
3.22
2.70
3.74
2.36
0.89
0.39
0.20
1.04
0.84
0.17
0.25
0.26
0.26
0.52
0.27
0.29
0.15
0.397
0.290
CN~
<0.10
-------
TABLE E-31. UNION STREET FEEDER LINE TO THE SOUTH NORTHSIDE INTERCEPTOR, SAMPLING DAY TWO
DAY OF
DATE WEEK TIME
8-22-78 T 6P
8P
10P
M 8-23-78 W 12A
i_n
2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.040
0.039
0.040
0.038
0.037
0.039
0.043
0.041
0.043
0.044
0.040
0.044
0.041
0.002
0.488
<0.001
<0.001
0.001
0,001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.002
<0.001
<0.002
0.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.041
0.087
0.209
0.127
0.143
0.102
0.166
0.137
0.093
0.108
0.128
0.124
0.122
0.042
<0.01
0.05
0.05
0.05
0.01
0.04
0.06
0.04
0.05
0.05
0.04
0.04
<0.05
0.16
0.01
0.02
0.02
0.03
0.03
0.02
0.02
0.01
0.01
0.02
0.02
0.02
0.02
0.01
1.57
3.86
3.59
0.61
1.21
0.97
1.63
1.45
2.04
1.42
1.68
2.02
1.84
0.97
1.251
1.25
.0.65
0.60
0.27
0.34
0.28
0.29
0.43
0.38
0.55
0.25
0.55
0.36
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
-------
TABLE E-32. UNION STREET FEEDER LINE TO THE SOUTH NORTHSIDE INTERCEPTOR, SAMPLING DAY THREE
DAY OP
DATE WEEK TIME
8-23-78 W 6P
8P
10P
12A
S 8-17-78 Th 2A
4A
6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.045
0.040
0.043
0.038
0.035
0.032
0.033
0.037
0.040
0.043
0.044
0.043
0.039
0.004
0.473
<0.001
<0.001
<0.001
<0.001
<0.00l
<0.001
0.001
<0.001
<0.001
0.001
<0.001
0.001
<0.001
0.000
METAL
Cr
0.138
0.132
0.279
0.143
0.082
0.044
0.174
0.112
0.139
0.156
0.148
0.107
0.143
0.056
AND CYANIDE CONCENTRATIONS
(mg/1)
Nl Pb Zn Cu
0.07
0.06
0.06
0.06
0.04
0.01
0.01
0.03
0.01
0.01
0.03
0.03
0.03
0.02
0.01
0.03
0.03
0.02
0.02
0.03
0.02
0.03
0.04
0.04
0.03
0.01
0.03
0.01
0.22
0.24
0.19
0.20
0.19
0.19
0.24
0.27
0.25
0.22
0.25
0.29
0.23
0.03
0.55
0.26
0.33
0.35
0.40
0.14
0.18
0.27
0.64
0.78
0.58
0.35
0.40
0.20
CN~
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
-------
TABLE E-33. OLD PARK ROAD TRUNKLINE, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
11-20-78 M
11-21-78 T
CTi
I-1
MEAN
STANDARD
MGD
6P
8P
10P
12A
2A
4A
6A
8A
10A
12P
2P
4P
DEVIATION
MILLION GAL
OF FLOW/2H
0.075
0.077
0.075
0.062
0.052
0.047
0.047
0.071
0.071
0.076
0.073
0.064
0.066
0.011
0.790
Cd
0,002
0,002
0.004
0.003
0,003
0.003
<0,001
0.001
0,002
0.076
0.002
0.001
10.00
0.021
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.002
0.048
0.130
0.050
0.093
0.068
0.017
0.075
0.061
0.711
0.828
0.068
0.18
0.28
6.25
6.75
4.42
4.30
5.95
9.57
9.94
10.08
7.90
8.98
7.39
6.46
7.33
2.01
0.02
0.01
0.01
0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
0.01
<0.02
0.01
0.26
0.16
0.23
0.15
0.13
0.13
0.09
0.21
0.18
0.20
0.23
0.21
0.18
0.05
0.13
0,07
0.14
0.09
0.07
0.06
0.03
0.12
0.11
0.10
0.11
0.09
0.09
0.03
CN~
0.15
o.io
-------
TABLE E-34. OLD PARK ROAD TRUNKLINE, SAMPLING DAY TWO
o\
DAY OF
DATE WEEK TIME
11-21-78 T
11-22-78 W
11-15-78 W
MEAN
STANDARD
MGD
6P
8P
10P
12A
2A
4A
6A
8A
10A
12P
2P
4P
DEVIATION
MILLION GAL,
OF FLOW/2H
0.067
0.071
0.068
0.058
0.058
0.050
0.054
0.068
0.064
0.064
0.067
0.071
0.063
0.007
0.753
»
Cd
<0.001
0.001
0.002
0.002
0.007
0.003
0.002
0.001
0.001
0.002
0.002
<0.001
<0.002
0.002
METAL AND CYANIDE CONCENTRATIONS
(rag/1)
Cr Ni Pb Zn Cu
0.094
0.047
0.047
0.075
0.211
0.034
0.126
0.615
0.036
0.040
0.051
0.024
0.12
0.17
4.40
3.24
3.49
4.75
6.87
2.59
14.28
9.16
6.42
9.03
1.48
0.61
5.53
3.87
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
<0.01
0.01
0.00
0.18
0.16
0.14
0.15
0.21
0.15
0.15
0.16
0.25
0.19
0.20
0.10
0.17
0.04
0.12
0.11
0.10
0.11
0.10
0.06
0.05
0.10
0.12
0.10
0.11
0.05
0.09
0.02
CN
0.10
0. 10
0. 10
0. 12
0. 10
0.10
0.10
<0.10
<0. 10
<0.10
<0. 10
<0.10
<0. 11
0. 01
LBS/DAY
<0.010 0.74 40.46 0.058 1.05 0.58 <0. 39
-------
DAY OF
DATE WEEK TIME
11-15-78 W 6P
8P
10P
11-16-78 TH 12A
2A
4A
N»
ui 6A
8A
10A
12P
2P
4?
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.071
.068
.067
.067
.056
.058
.062
.075
.064
.067
.068
.068
.066
.005
.791
>
Cd
<0
0
0
<0
<0
<0
0
0
<0
<0
0
0
<0
0
.001
.001
,001
,001
,001
.001
.001
.001
.001
.001
.001
.007
.002
.002
METAL AND CYANIDE CONCENTRATIONS
(n»g/l)
Cr Nl Pb Zn Cu
0.015
0.003
0.006
0.033
0.047
0.066
0.047
0.027
0.034
0.021
0.029
0.040
0.031
0.018
0.4'3
0.90
0.80
0.73
0.71
0.91
0.55
0.48
0.33
0.25
0.24
1.05
0.62
0.27
<0.01
0.01
0.02
0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
0.01
j<0.02
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.06
.14
.13
.14
.13
.11
.08
.13
.10
.07
.17
.47
.14
.11
0.03
0.09
0.09
0.07
0.06
0.03
0.04
0.08
0.08
0.06
0.10
0.11
0.07
0.02
CN~
0.10
0.10
0.10
0.10
<0.10
0.14
0.19
<0.10
0.13
<0.1Q
o.u
o.io
-------
TABLE E-36. PETE'S RUN INTERCEPTOR TRUNKLINE, SAMPLING DAY ONE
DAY OF
DATE WEEK TIME
2-19-79 M 6P
8P
10P
2-20-79 T 12A
2A
O
TV
* 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
120
120
120
120
100
082
082
180
180
180
137
107
127
036
528
Cd
0.
o:
0.
o,
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
002
001
002
050
001
001
001
001
001
001
002
003
006
014
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.009
0.008
0.025
0.086
0.016
0.011
0.008
0.027
0.006
0.007
0.010
0.014
0.019
0.022
0.03
0.04
0.18
0.31
0.07
0.06
0.03
0.03
0.01
0.02
0.03
0.03
0.07
0.09
0.02
0.02
0.07
0.24
0.04
0.04
0.01
0.02
0.01
0.02
0.02
0.03
0.05
0.06
0.25
0.15
0.27
5.11
0.27
0.16
0.06
0.08
0.09
0.13
0.19
0.04
0.57
1.43
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
24
21
51
38
24
20
12
17
18
22
21
16
24
11
CN~
<0.10
0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
0.00
LBS/DAY
0.067 0.24 0.85 0.54 6.86 2.98 <1.27
-------
TABLE E-37. PETE'S RUN INTERCEPTOR TRUNKLINE, SAMPLING DAY TWO
N)
; DAY OF
DATE WEEK TIME
"< 6-26-79 T 6P
r 8P
10P
-4
~: 6-27-79 W 12A
2A
4A
j
" 6A
8A
10A
12P
2P
4P
MEAN
STANDARD DEVIATION
MGD
MILLION GAL.
OF FLOW/2H Cd
0.088
0.089
0.087
0.084
0.064
0.051
0.049
0.058
0.089
0.098
0.104
0.100
0.080
0.019
0.961
0,001
0.033
0.002
0.001
0.003
<0.001
0.002
<0.001
0.002
0.004
0.009
0.002
10.005
0.009
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Ni Pb Zn Cu
0.008
0.195
0.022
0,017
0,008
0.007
0.005
0.006
0.003
0.008
0.014
0.017
0.026
0.054
0.02
0.34
0.04
0,04
0.02
0.02
0.01
0.02
0.01
0.03
0.03
0.04
0.05
0.09
0.02
0.49
0.04
0.03
0.02
0.01
0.01
0.02
0.02
0.04
0.03
0.04
0.06
0.13
0.27
4.64
0.31
0.19
0.13
0.24
0.13
0.20
0.20
0.26
0.33
0.22
0.59
1.28
0.15
0.77
0.18
0.17
0.13
0.11
0.11
0.08
0.11
0.18
0.19
0.20
0.20
0.18
CN
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
o.io
-------
TABLE E-38. PETE'S RUN INTERCEPTOR TRUNKLINE, SAMPLING DAY THREE
DAY OF
DATE WEEK TIME
6-27-79 W
6-28-79 TH
o\
CTv
3C
CO
,?
1
*-*
~ MEAN
§ STANDARD
§ MGD
6P
8P
10P
12A
2A
4A
6A
8A
10A
12P
2P
4P
DEVIATION
MILLION GAL.
OF FLOW/2H
0.090
0.118
0.112
0.107
0.106
0.082
0.059
0.089
0.124
0.132
0.147
0.163
0.111
0.029
1.329
Cd
0.003
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
o.ooi
0.002
0.003
0.002
0.001
METAL AND CYANIDE CONCENTRATIONS
(mg/1)
Cr Nl Pb Zn Cu
0.018
0.019
0.019
0.019
0.014
0.014
0.010
0.012
0.013
0.017
0.023
0.014
0.016
0.004
0 ,'0'3
0.11
0.11
0.10
0.09
0.10
0.02
0.09
0.10
0.11
0.11
0.03
0.083
0.035
0.05
0.09
0.11
0.09
0.07
0.07
0.03
0.09
0.09
0.07
0.07
0.03
0.072
0.025
0.42
0.41
0.35
0.19
0.26
0.20
0.04
0.17
0.25
0.19
0.29
0.04
0.23
0.13
0.18
0.29
0.34
0.26
0.23
0.26
0.16
0.19
0.26
0.27
0.44
0.16
0.25
0.08
CN~
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
7 OO
LBS/DAY
0.018 0.18 0.95 0.80
2.61
2.89
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
|3. RECIPIENT'S ACCESSIOf*NO.
AND SUBTITLE
SOURC£S AND FLOWS IN A
MUNICIPAL SEWAGE SYSTEM
5. REPORT DATE
August 1981 (Issuing Date)
iterature Survey & Field Investigation of the Kokomo,
Indiana, Sewage System _ _
S. PERFORMING ORGANIZATION CODE
7. AUTHORISJ
K. J. Yost, R. F. Wukasch, T. G. Adams,
Bert Michalczyk
3. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
The Purdue Research Foundation
Purdue University
West Lafayette, Indiana 47907
TO. PROGRAM ELEMENT NO.
AZB1B
AE/05
11. CONTRACT/GRANT NO.
R-805631
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Municipal Environmental Research Laboratory
Office of Research & Development, USEPA
Cincinnati, Ohio 45268
Final. 10/77 to 1/81
14. SPONSORING AGENCY CODE
15, SUPPLEMENTARY NOTES
Project Officer - S. A., Hannah
(513/684-7651)
6. ABSTRACT
-The flow of heavy metals (Cu, Nf, Cr, Cd, Zn, PB) and cyanide in the Kokomo,
Indiana, collection system and wastewater treatment plant is analyzed. The primary
objective is to determine the relative contributions of domestic and non-domestic
sources to the total pollutant load in the system, and to assess the levels of-dis-
charge control required for the disposal of municipal sludge by landfill or agri-
cultural landspreading. Sampling was conducted at point source locations, in major
sewer trunk- and feeder lines, and at the treatment plant. Production and'waste
treatment data are presented for point sources sampled for the purpose of character-
izing metal and cyanide discharges as a function of these parameters. A heavy metals
mass balance is attempted for the treatment plant. Metal removal factors are pre-
sented for various plant operations.
A simple statistical approach is presented for the design of a cost-effective
sampling program for correlating point source and trunkline pollutant sampling.
The purpose is to minimize the amount of sampling required to account for pollutants
seen in trunkline and treatment plant streams in terms of discharges from specific
point sources.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.lDENTIFtERS/OPEN SNOED TERMS
COSAT1 Field/Group
Water Pollution
Waste Treatment
Industrial Wastes
Sludge Disposal
Metal Wastes
Sludge Spreadin-g
Land Application
Sewer Sampling
Agricultural landspread-
ing
13 8
13. OraTrUSUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (Thts Report)
UNCLASSIFIED
21. NO. Of PAGcS
267
20. SECURITY CLASS (Thu page!
UNCLASSIFIED
22. PRICE
-------
|