EPA 440/1 -76/060 J
Group II
Development Document for Interim
Final Effluent Limitations Guidelines
and Proposed New Source Performance
Standards for the
Photographic Processing
Subcategory
of the
Photographic
Point Source Category
\
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
JULY 1976
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DEVELOPMENT DOCUMENT
for
INTERIM FINAL
EFFLUENT LIMITATIONS, GUIDELINES
AND PROPOSED NEW SOURCE PERFORMANCE STANDARDS
for the
PHOTOGRAPHIC PROCESSING SUBCATEGORY
of the
PHOTOGRAPHIC POINT SOURCE CATEGORY
Russell E. Train
Administrator
Andrew W. Breidenbach, Ph.D.
Assistant Administrator
for Water and Hazardous Materials
Eckardt C. Beck
Deputy Assistant Administrator for
Water Planning and Standards
Robert B. Schaffer
Director, Effluent Guidelines Division
Joseph S. Vitalis
Project officer
and
George M. Jett
Assistant Project Officer
July 1976
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20U60
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ABSTRACT
This document presents the findings of a study of the
photographic processing subcategory of the photographic
point source category for the purpose of developing effluent
limitations and guidelines for existing point sources and
standards of performance and pretreatment standards for
existing sources and for new sources, to implement Sections
301 (b) , 301(c), 30«»(b), 304 (c) , 306 (b) , 307 (b) , and 307 (c)
of the Federal Water Pollution Control Act, as amended (33
U.S.C. 1251, 1311, 131U(b) and (c) , 1316 (b) and 1317(b) and
(c) , 86 Stat. 816 et. seq.) (the "Act").
Effluent limitations and guidelines contained herein set
forth the degree of effluent reduction attainable through
the application of the Best Practicable Control Technology
Currently Available (BPT) and the degree of effluent
reduction attainable through the application of the Best
Available Technology Economically Achievable (BAT) which
must be achieved by existing point sources by July 1, 1977,
and July 1, 1983, respectively. The standards of per-
formance and pretreatment standards for existing and new
sources contained herein set forth the degree of effluent
reduction which is achievable through the application of the
Best Available Demonstrated Control Technology (NSPS),
processes, operating methods, or other alternatives.
The development of data and recommendations in this document
relate to the photographic processing point source category
which is one of eight industrial segments of the
miscellaneous chemicals point source category. Effluent
limitations were developed for a single subcategory covering
the photographic processing industry on the basis of the
level of raw waste load as well as on the degree of
treatment achievable by suggested model systems. These
systems include biological and physical/chemical treatment
and systems for reduction in pollutant loads. Various
combinations of in-plant and end-of-pipe technologies are
considered for photographic processing laboratories
(plants) .
Supporting data and rationale for development of the
proposed effluent limitations, guidelines and standards of
performance for the photographic processing subcategory of
the photographic point source category are contained in this
report.
111
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TABLE OF CONTENTS
Section Title Page
Abstract
Table of Contents
List of Figures
List of Tables
I Conclusions
II Recommendations
III Introduction
IV Industrial Categorization
V Waste Characterization
VI Selection of Pollutant Parameters
VII Control and Treatment Technologies
VIII Cost, Energy, and Non-water Quality
Aspects
IX Best Practicable Control Technology
Currently Available (BPT)
X Best Available Technology Economically
Achievable (BAT)
XI New Source Performance Standards (NSPS)
XII Pretreatment Standards
XIII Performance Factors for Treatment Plant
Operations
XIV Acknowledgements
XV Bibliography
XVI Glossary
XVII Abbreviations and Symbols
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LIST OF FIGURES
Number
IV-1
IV-2
IV-3
iv-a
IV-5
IV-6
VIII-1
VIII-1a
VIII-2A
VIII-2B
VIII-2C
VIII-3
VIII-H
VIII-5
VIII-6
VIII-7
VIII-8
Title
Page
Black and White Film Processing
Reversal Black and White Film Processing
Color Negative Film Processing
Color Reversal Processing
(Incorporated Couplers)
Color Reversal Processing
(Couplers in Developer)
Typical Photographic Processing
Flow Diagram
Biological Wastewater Treatment
Cost Model Flow Sheet
In-Plant BPT Treatment Cost
Model Flow Sheet
BAT/NSPS Wastewater Treatment Cost Model
Cyanide Destruct Flow Sheet
BAT Wastewater Treatment Cost Model
Filtration Flow Sheet
BAT/NSPS Wastewater Treatment Cost Model
Ion Exchange Flow Sheet
Equalization Basin/Cost Curve No. 1
Aeration Basin/Cost Curve No. 5
Fixed-Mounted Aerators/Cost Curve No. 5B
Primary and Secondary Clarifier/Cost
Curve No. 2, 6
Sludge Thickeners Including Mechanism/Cost
Curve No. 7
Multi-Media Filters Including Feedwell,
Pumps and Sump/Cost Curve No. 10
Vll
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LIST OF TABLES
Number Title Page
1-1 Summary Table - RWL's and Long-Term Daily
Effluents
II-1 BPT Effluent Limitations Guidelines
II-2 BAT and NSPS Effluent Limitations
Guidelines
III-1 Photographic Studies, Portrait - SIC 7221
II1-2 Commercial Photography, Art, and
Graphics - SIC 7333
III-3 Photofinishing Laboratories - SIC 7395
III-H Services Allied to Motion Picture
Production - SIC 7819
IV-1 Plant Size From 200 Plant Survey
Summary Data
IV-2 Bleach Bath Composition
IV-3 Statistical Analysis of NAPM/Field
Survey - Spring 1976
V-1 Raw Waste Loads - Overall Photographic
Processing Industry
V-2 Calculated RWL for Typical Photographic
Processes
VI-1 List of Parameters to be Examined
VI-2 Summary Data for Kodak King's Landing Plant
VII-1 Waste Disposal Methods in the Photographic
Processing Industry
VII-2 Squeegee Summary
VII-3 Summary of Ozonization Results
VII-4 Feasibility of Treating Photographic
IX
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Processing Chemicals With Activated Carbon
VIII-1
VIII-2
VIII-3
VIII-U
VIII-5
VIII-5a
VIII-6
VIII-6a
VIII-7
VIII-8
IX-1
X-1
XI-1
XII-1
XIII-1
XVIII
Biological Treatment System Design
Summary
BAT Treatment System Design Summary
Wastewater Treatment Costs for BPT,
NSPS and BAT Effluent Limitations
(5,000 sq.ft./day Production Rate)
Wastewater Treatment Cost for BPT, NSPS
and BAT Effluent Limitations (50,000 sq.ft/
day Production Rate)
Summary of Capital Costs for Wastewater
Treatment (Biological Plus In-Plant
Model 5,000 sq ft/day)
Summary of Capital Costs for Wastewater
Treatment (In-Plant BPT Model 5,000
sq. ft/day)
Summary of Capital Costs for Wastewater
Treatment (Biological Plus In-Plant
Model 50,000 sq. ft/day)
Summary of Capital Costs for Wastewater
Treatment (In-Plant BPT Model 50,000
sq. ft/day)
Summary of Capital Costs for Wastewater
Treatment (BAT and NSPS Model 5,000 sq.ft/day)
Summary of Capital Costs for Wastewater
Treatment (BAT and NSPS Model 50,000 sq.ft/day)
BPT Effluent Limitations Guidelines
BAT Effluent Limitations Guidelines
New Source Performance Standards
Pretreatment Unit Operations
Peformance Factor Summary
Metric Table
x
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SECTION I
CONCLUSIONS
General
The miscellaneous chemicals manufacturing ppint source
category encompasses, eight segments, grouped together for
administrative jpurposes. This document provides background
information for the photographic processing subcategory of
the photographic point source category and represents a
revision of a portion of the initial contractor's draft
document issued in February, 1975.
In that document it was pointed out that each segment
differs from the others in raw materials, manufacturing
processes, and final products. Water usage and subsequent
wastewater discharges also were found to vary considerably.
Consequently, for the purpose of the development of the
effluent limitations and guidelines for corresponding BPT
(Best Practicable Control Technology Currently Available),
NSPS (Best Available Demonstrated Control Technology) for
new sources, and BAT (Best Available Technology Economically
Achievable) requirements, each segment is treated
independently.
The diversity of products and manufacturing operations to be
covered indicates the need for separate effluent limitations
for (segments of the industry) industries, and these are
presented in separate development documents for each segment
of the miscellaneous chemicals point source category. This
development document deals only with the photographic
processing industry.
The photographic processing subcategory of the photographic
point source category is defined to include commodities
listed under Standard Industrial Classifications (SIC) 7221,
7333, 7395 and 7819.
It should be emphasized that the proposed treatment model
technology is used only as a guideline and to establish a
cost basis. The model may not be the most appropriate in
every case. The cost models for BPT, BAT, and NSPS were
developed to facilitate the economic analysis and should not
be construed as the only technology capable of meeting the
effluent limitations, guidelines and standards of
performance presented in this development document. There
are many alternative systems which, taken either singly or
in combination, are capable of attaining the effluent
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limitations, guidelines and standards of performance
recommended in this development document. These alternative
choices include:
1. Various types of end-of-pipe wastewater treatment.
2. Various in-plant modifications and installation of
at-source pollution control equipment.
3. Various combinations of end-of-pipe and in-plant
technologies.
It is the intent of this study to allow the individual plant
to make the choice of what specific combination of pollution
control measures is best suited to its situation in
complying with the limitations and standards of performance
presented. To avoid substantial economic injury to small
business concerns, a size exemption for photographic
processing plants handling 150 square meters per day (1,600
square feet per day) of film and paper will be established
by the Agency.
Photographic Processing
The photographic processing subcategory of the photographic
point source category was not further subcategorized for the
purpose of effluent limitations, guidelines and new source
performance standards. Additional subcategorization was
deemed unnecessary because the pollutants in the wastewaters
were the same and the pollutant loadings per unit of
production were in a relatively narrow range in the plants
surveyed. This document represents the photographic
processing portion of the photographic point source
category. As time and resources permit, the additional
segments of this category such as the manufacture of
photographic film, photographic plates and photographic
paper will be promulgated.
The major sources of wastewater in the photographic
processing subcategory are photoprocessing solution
overflows and wash waters. Wastewaters generated by this
segment of the industry can be characterized as containing
high concentrations of BODJ5, COD, TOC, silver and cyanides
in various forms.
Existing control and treatment technology, as practiced in
the category, includes primarily in-plant pollutant
reductions for silver and cyanides through recovery of
bleaches and silver which is widely practiced for economic
reasons. An estimate of 95% of all photographic processing
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plants discharge their wastewaters to municipal sewer
systems; only one plant visited had any end-of-pipe
treatment facility, a 20,000-gpd capacity pilot biological
treatment system to investigate the treatability of its
wastewaters.
Effluent limitations and guidelines have been established
for silver and total cyanides. The choice of these
parameters was based on economic considerations.
Furthermore, these pollutants may exert a toxic effect on a
biological treatment process and are the major contaminants
in the photographic processing wastewaters.
The treatment models recommended to attain each of the three
levels of treatment technology are:
Technology Level End-of-pipe Treatment Model
BPT In-plant modifications
NSPS BPT plus cyanide destruction,
dual-media filtration and
ion exchange for silver removal
BAT BPT plus cyanide destruction,
dual-media filtration and
ion exchange for silver removal
It is emphasized that in-plant measures to reduce silver and
ferrocyanide concentrations as well as end-of-pipe treatment
methods are included as part of the recommended treatment
technologies as these are currently in wide use in the
industry.
In conclusion, effluent limitations guidelines were derived
on the basis of the maximum for any one day (maximum day
limitation) and the average of daily values for any period
of thirty consecutive days (maximum thirty day limitation).
Since no long-term data for exemplary treatment were
uncovered in the photographic processing industry during
this study, the factors used in deriving these time-based
limitations were derived from generally accepted and
achievable variability factors for the physical/chemical
treatment systems evaluated in the electroplating point
source category. The paucity of end-of-pipe wastewater
treatment systems in the photographic processing industry
led to the decision to use performance factors from a
category that had similar wastewater treatment systems.
Hence, the performance factors used from the electroplating
point source category were applied to both the in-plant BPT
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Table I -i
'Summary Tcb'c
Photographic Processing Industry
8PCTCA (19771 (BPT)
S'jbcategory
%
Entire Industry
£>.
Contami nants
of Interest Flow
L/l ,000 sq. m
(gal/1,000 sq.ft.)
BOD., COO, TOC, , 163,000
TSS, TKN, IDS, (4,000)
Si Iver, Ferro-
cyani de
Parameter
BOD.
COO
-
ta (Silver)
CN (TotaJ)
RWl
kg/1 ,000 sq. m
(lbs./l,OCO sq.ft.;
36.7
(7.5 )
123.0
(25.1)
0.07
(0;015)
.0.39
(C.O19)
mg/L
225
752
0.45
0.57
Treatment
Technology
Long-Term Oji 1y
Effluent
Parameter kg/1,000 sq. m
Regeneration
of Bleach
and Silver
Recovery
(lbs./l,000
Ag (Silver) °-07
(0.015)
CN (Total) °-09
(0.019)
sq.ft.)
BAT (1983)
New Source Perform^•:e Standards (NSPS)
Subeategory
Entire Industry
Treatment
Technology
Oxidation,
Filtration, and
Ion Exchange
lorq-Tern Daily Effluen
Parameter kg/1,000 sq. n
(lbs./l,000 sq. ft.
Ag (Silver) .0016
.00034)
CN (Total) 0.038
rn "ii7)
Treatment
Technol oqy
Oxidation,
Filtration, and
Ion Exchange
Lonq-Term na; ly E
Parameter kg/I, 000 sq
(lbs./l,000 sq
Ag (Silver) -0016
.00034)
CN (Total) -008
.001?)
ffluent
. rn
. ft.)
6/30/76
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treatment, which utilizes bleach regeneration and
electrolytic silver recovery, and to BAT/NSPS
physical/chemical treatment steps consisting of • cyanide
destructioo, dual-media filtration and ion exchange for
silver removal.
Table 1-1 summarizes the contaminants of interest, raw waste
loads, and recommended treatment technologies for BPT, BAT,
and NSPS for the photographic processing subcategory of the
photographic point source category.
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SECTION II
RECOMMENDATIONS
General
The recommendations for effluent limitations and guidelines
commensurate with the BPT, BAT and NSPS are presented in the
following text. A discussion of in-plant and end-of-pipe
controls technology required to achieve the recommended
effluent limitations, guidelines and new source performance
standards are included. The NSPS for new sources includes
the most exemplary process controls.
Photographic Processing
The BPT, BAT, and NSPS effluent limitations proposed for the
photographic processing industry are presented in Tables II-
1 and II-2. These effluent limitations guidelines are based
on the maximum day limitation and the maximum thirty day
limitation. These effluent limitation values are developed
using the performance factors for the treatment plant
operation as discussed in Section XIII of this development
document.
Wastewaters subject to these limitations include all process
wastewaters, but do not include sanitary wastewaters.
Implicit in the recommended guidelines for the photographic
processing subcategory of the photographic point source
category is the use of in-plant control measures to reduce
silver and cyanide. In-plant modifications will lead to
reductions in wastewater flow, increased quantity of water
used for recycle, and improvement in raw wastewater quality.
In-plant treatment technologies described in Section VIII
should be utilized by the photographic processing
subcategory to achieve BPT effluent limitations and
guidelines.
To meet BAT and NSPS effluent limitations and new source
performance standards treatment technologies equivalent to
in-plant BPT treatment followed by cyanide destruction,
dual-media filtration and ion exchange for silver removal
are recommended.
After varying degrees of in-plant pollution abatement
measures which serve as a pretreatment step most
photographic processing plants discharge their effluents to
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Table II-l
BPT Effluent Limitations Guidelines
Photographic Processing Industry
Subcategory
Entire
Industry
Effluent
Characteristic
Ag (Silver)
CN (Total)
Effluent Limitations
Average of Daily Values
'for 30 Consecutive Days
Shall not exceed
kg/1,000 m^
(lb/1,000 ft2)
0.07
(0.015)
0.09
(0.019)
Maximum for
Any one day
kg/1,000 m^
(lb/1,000 ft2)
0.14
(0.030)
0.18
(0.038)
00
6/30/76
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Table II -2
BAT and NSPS Effluent Limitations Guidelines
Photographic Processing Industry
Effluent Limitations
Subcategorv
Entire
Industry
Effluent
Characteristic
Ag (Silver)
CN (Total)
Average of Dally Values
for 30 Consecutive Days
Shall not Exceed
kg/1,000 m2
(Ib 1,000 ft2)
0.0016
(0.00034)
0.008
(0.0017)
Maximum for
Anv Orte Dav
kg/1,000 m2
(lb/1,000 ft2)
0.0032
(0.00067)
0.016
(0.0034)
6/30/76
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municipal sewer systems. Certain constituents (i.e., silver
and cyanide) which could exert toxic effects on a biological
system and various non-biodegradable material may also be
present. Therefore, in-plant measures or pretreatment to
reduce the concentrations of such contaminants to levels
acceptable to local authorities must be utilized.
10
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SECTION III
INTRODUCTION
Purpose and Authority
The Federal Water Pollution Control Act Amendments of 1972
(the Act) made a number of fundamental changes in the
approach to achieving clean water. One of the most
significant changes was to shift from a reliance on effluent
limitations related to water quality to a direct control of
effluents through the establishment of technology-based
effluent limitations to form an additional basis, as a
minimum, for issuance of discharge permits.
The Act requires EPA to establish guidelines for technology-
based effluent limitations which must be achieved by point
sources of discharges into the navigable waters of the
United States. Section 301(b) of the Act requires the
achievement by not later than July 1, 1977 of effluent
limitations for point sources, other than publicly owned
treatment works, which are based on the application of the
BPT as defined by the Administrator pursuant to Section
304 (b) of the Act. Section 301(b) also requires the
achievement by not later than July 1, 1983 of effluent
limitations for point sources, other than publicly owned
treatment works, which are based on the application of the
BAT, resulting in progress toward the national goal of
eliminating the discharge of all pollutants, as determined
in accordance with regulations issued by the Administrator
pursuant to Section 304(b) of the Act. Section 306 of the
Act requires the achievement by new sources of federal
standards of performance providing for the control of the
discharge of pollutants, which reflects the greatest degree
of effluent reduction which the Administrator determines to
be achievable through the application of the NSPS process,
operating methods, or other alternatives, including, where
practicable, a standard permitting no discharge of
pollutants.
Section 304(b) of the Act requires the Administrator to
publish regulations based on the degree of effluent
reduction attainable through the application of the BPT and
the best control measures and practices achievable,
including treatment techniques, process and procedure
innovations, operation methods, and other alternatives. The
regulations proposed herein set forth effluent limitations
guidelines pursuant to Section 304(b) of the Act for the
photographic processing subcategory of the photographic
11
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point source category. Section 304(c) of the Act requires
the Administrator to issue information on the processes,
procedures, or operating methods which result in the
elimination or reduction in the discharge of pollutants to
implement standards of performance under Section 306 of the
Act. Such information is to include technical and other
data, including costs, as are available on alternative
methods of elimination or reduction of the discharge of
pollutants.
Section 306 of the Act requires the Administrator, within
one Year after a category of sources is included in a list
published pursuant to Section 306 (b) (1) (A) of the Act, to
propose regulations establishing federal standards of
performance for new sources within such categories. The
Administrator published in the Federal Register of January
16, 1973 (38 F.R. 1621) a list of 27 source categories.
Publication of the list constituted announcement of the
Administrator's intention of establishing, under Section
306, standards of performance applicable to new sources.
Furthermore, Section 307(b) provides that:
1. The Administrator shall, from time to time, publish
proposed regulations establishing pretreatment
standards for introduction of pollutants into
treatment works (as defined in Section 212 of this
Act) which are publicly owned, for those pollutants
which are determined not to be susceptible to
treatment by such treatment works or which would
interfere with the operation of such treatment
works. Not later than ninety days after such
publication, and after opportunity for public hear-
ing, the Administrator shall promulgate such
pretreatment standards. Pretreatment standards
under this subsection shall specify a time for
compliance not to exceed three years from the date
of promulgation and shall be established to prevent
the discharge of any pollutant through treatment
works (as defined in Section 212 of this Act) which
are publicly owned, which pollutant interferes
with, passes through, or otherwise is incompatible
with such works.
2. The Administrator shall, from time to time, as
control technology, processes, operating methods,
or other alternatives change, revise such
standards, following the procedure established by
this subsection for promulgation of such standards.
12
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3. When proposing or promulgating any pretreatment
standard under this section, the Administrator
shall designate the category or categories of
sources to which such standard shall apply.
<*. Nothing in this subsection shall affect any
pretreatment requirement established by any State
or local law not in conflict with any pretreatment
standard established under this subsection.
In order to insure that any source introducing pollutants
into a publicly owned treatment works, which would be a new
source subject to Section 306 if it were to discharge
pollutants, will not cause a violation of the effluent
limitations established for any such treatment works, the
Administrator is required to promulgate pretreatment
standards for the category of such sources simultaneously
with the promulgation of standards of performance under
Section 306 for the equivalent category of new sources.
Such pretreatment standards shall prevent the discharge into
such treatment works of any pollutant which may interfere
with, pass through, or otherwise be incompatible with such
works.
The Act defines a new source to mean any source the
construction of which is commenced after the publication of
proposed regulations prescribing a standard of performance.
Construction means any placement, assembly, or installation
of facilities or equipment (including contractual obliga-
tions to purchase such facilities or equipment) at the
premises where such equipment will be used, including
preparation work at such premises.
Methods Used for Development of the Effluent Limitations and
Standards for Performance
The effluent limitations, guidelines and standards of
performance proposed in this document were developed in the
following manner. The miscellaneous chemicals manufacturing
point source category was first divided into industrial
segments, based on type of manufacturing and products
manufactured. Determination was then made as to whether
further subcategorization would aid in description of the
category. Such determinations were made on the basis of raw
materials required, products manufactured, processes
employed, and other factors.
The raw waste characteristics for each category and/or
subcategory were then identified. This included an analysis
of: 1) the source and volume of water used in the process
13
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employed and the sources of wastes and wastewaters in the
plant; and 2) the constituents of all wastewaters
(including toxic constituents) which result in taste, odor,
and color in water. The constituents of wastewaters which
should be subject to effluent limitations, guidelines and
standards of performance were identified.
The full range of control and treatment ^technologies
existing within each category and/or subcategory was
identified. This in'cluded an identification of each dis-
tinct control and treatment technology, including both in-
plant and end- of-pipe technologies, which are existent or
capable of being designed for each subcategory or category.
It also included an identification of the effluent level
resulting from the application of each of the treatment and
control technologies, in terms of the amount of constituents
and of the chemical, physical, and biological
characteristics of pollutants. The problems, limitations,
and reliability of each treatment and control technology and
the required implementation time were also identified. In
addition, the non-water quality environmental impacts (such
as the effects of the application of such technologies upon
other pollution problems, including air, solid waste,
radiation, and noise) were also identified. The energy
requirements of each of the control and treatment
technologies were identified, as well as the cost of the
application of such technologies.
The information, as outlined above, was evaluated in order
to determine what levels of technology constituted the BPT,
BAT, and NSPS, In identifying such technologies, factors
considered included the total cost of application of
technology in relation to the effluent reduction benefits to
be achieved from such application, the age of equipment and
facilities involved, the process employed, the engineering
aspects of the application of various types of control
techniques, process changes, non-water quality environmental
impact (including energy requirements), and other factors.
During the initial phases of the study, an assessment was
made of the availability, adequacy, and usefulness of all
existing data sources. Data on the identity and performance
of wastewater treatment systems were known to be included
in:
1. NPDES permit applications.
2. Self-reporting plant discharge data from
various states.
14
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3. Surveys conducted by trade associations or by
agencies under research and development grants.
A preliminary analysis of these data indicated an obvious
need for additional information.
Additional data in the following areas were required: 1)
process raw waste load (RWL) related to production; 2)
currently practiced or potential in-process waste control
techniques; and 3) the identity and effectiveness of end-of-
pipe treatment systems. The best source of information was
the manufacturers themselves. Additional information was
obtained from direct interviews and sampling visits to
production facilities.
Collection of the data necessary for development of RWL and
effluent treatment capabilities within dependable confidence
limits required analysis of both production and treatment
operations. In a few cases, the plant visits were planned
so that the production operations of a single plant could be
studied in association with an end-of-pipe treatment system
which receive only the wastes from that production. The RWL
for this plant and associated treatment technology would
fall within a single subcategory. However, the wide variety
of products manufactured by most of the industrial plants
made this situation rare.
In the majority of cases, it was necessary to visit facili-
ties where the products manufactured fell into several
subcategories. The end-of-pipe treatment facilities
received combined wastewaters associated with several
subcategories (several products, processes, or even
unrelated manufacturing operations) . It was necessary to
analyze separately the production (waste-generating)
facilities and the effluent (waste treatment) facilities.
This approach required establishment of a common basis, the
raw waste load (RWL), for common levels of treatment
technology for the products within a subcategory and for the
translation of treatment technology between categories
and/or subcategories.
The selection of wastewater treatment plants was developed
from information available in the NPDES permit applications,
state self-reporting discharge data, and contacts within the
segment. Every effort was made to choose facilities where
meaningful information on both treatment facilities and
manufacturing processes could be obtained. Plants were
selected for visits as being representative of the category.
15
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Survey teams composed of project engineers and scientists
conducted the actual plant visits. Information on the
identity and performance of wastewater treatment systems was
obtained through:
1. Interviews with plant water pollution control
personnel or engineering personnel.
2. Examination of treatment plant design and
historical operating data (flow rates and analyses
of influent and effluent).
3. Treatment plant influent and effluent sampling.
Information on process plant operations and the associated
RWL was obtained through:
1. Interviews with plant operating personnel.
2. Examination of plant design and operating data
(design specification, flow sheets, day-to-day
material balances around individual process modules
or unit operations where possible).
3. Individual process wastewater sampling and
analysis.
4. Historical production and treatment data.
The data base obtained in this manner was then utilized by
the methodology previously described to develop recommended
effluent limitations, guidelines and standards of
performance for the photographic processing subcategory of
the photographic point source category. All of the
references utilized are included in Section XV of this
report. The data obtained during the field data collection
program are included in Supplement B. Cost information are
available in Supplement A. These documents are available
for examination by interested parties at the EPA Public
Information Reference Unit, Room 2922, (EPA Library),
Waterside Mall, 401 M St., S.W., Washington, D.C. 20460.
Photographic Processing Industry
Scope of the Study
For the purposes of this study, the photographic processing
subcategory of the photographic point source category was
defined to include all film processing activities listed
under SIC 7221 (Photographic Studios, Portrait), SIC 7333
16
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(Commercial Photography, Art, and Graphics), SIC 7395
(Photofinishing Laboratories), and SIC 7819 (Developing and
Printing of Commercial Motion Picture Film). Lists of the
specific services covered by these Standard Industrial
Classifications are presented in Tables III-1, III-2, III-3,
and II1-4.
The photographic processing subcategory of the photographic
point source category is made up of industrial and
commercial laboratories serving both the photographic trade
and the general public in film developing, photoprinting,
and enlarging. Photographic processing plants vary greatly
in size and are subject to seasonal variations in
production, nevertheless the waste loads are similar in
quality and quantity per unit of production.
Technical Approach to the Development of Effluent
Limitations Guidelines
The effluent limitations, guidelines and standards of
performance recommended in this document for photographic
processing were developed as described above. The technical
approach specific to photographic processing is described
below:
1. Plants were selected for visits as being
representative of the subcategory. The purpose of the plant
visits were threefold. First, the individual processes for
black and white and color film and paper within the plants
were investigated for familiarization with process concepts.
At this time, valuable information, otherwise unavailable,
was obtained on the various processes. Secondly, the
purpose was to investigate treatment technology, if any
existed. Lastly, and most importantly, the purpose was to
verify existing plant data on wastewater discharges with
analytical data measured on the site visits.
2. The raw waste loads (RWL) were determined from
field measurements taken on three photographic processing
plants visited and data received on Eastman Kodak plant
located on the west coast. Data supplied by the Eastman
Kodak Company was also used to substantiate the field survey
data. There was very strong similarity in the RWL's
determined for the three plants.
3. Effluent limitations, guidelines and new source
performance standards were developed by applying an end-of-
pipe treatment model to the raw wastewater and were
developed for the subcategory as a whole. Studies indicated
there was no need to impose different levels of treatment
17
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Table I I I -1
Photographic Studios, Portrait - SIC 7221
Home Photographers
Passport Photographers
Portrait Photographers
School Photographers
Transient Photographers
Table 111-2
Commercial Photography, Art, and Graphics - SIC 7333
Commercial Photography
Photographic Studios, Commercial
Table I I I -3
Photofinishing Laboratories - SIC 7395
Developing and printing of film, except commercial
motion picture film
Developing and processing of home movies
Film processing, except for the motion picture industry
Photograph developing and retouching
Photographic laboratories (not manufacturing)
Table I I I -k
Services Allied to Motion Picture Production - SIC 7819
Developing and printing of commercial motion picture film
18
6/30/76
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within the photographic processing subcategory. Effluent
limitations have been developed for silver and cyanide based
on the removal rate attained by widely used and generally
available in-plant treatment systems. For BAT/NSPS the
wastewater treatment technology and systems utilized in the
electroplating point source category are transferred to this
industry. Cyanide destruction by alkaline chlorination and
silver removal by ion exchange are the particular waste
treatment models used. Refer to Section VIII for detailed
design consideration.
Scope of Coverage for Data Base
Although there are an estimated 12,500 photographic
processing plants in the United States, only 650 of these
facilities are considered major laboratories with
significant wastewater discharges. In order to obtain the
information required to establish realistic effluent
limitations, sampling surveys were conducted at three photo-
processing plants by the EPA contractor. Since limited
information was available on the treatment of
photoprocessing wastes, a fourth plant was visited which had
a pilot biological treatment plant in operation at the time
of the survey. A special field survey of 30 non-Kodak
photographic processing plants was conducted by NAPM in the
spring of 1976 utilizing Kodak field teams. Data for flow,
BOD5_ and COD resulting from this effort plus data from 6
Kodak plants collected in the past three years were merged
with the 4 plants sampled by the EPA contractor. The
weighted averages for these three parameters were used to
build the RWL*s reported in Table V-1. In addition to the
field surveys, supplemental historical data compiled by the
Eastman Kodak Company for approximately 200 photoprocessing
plants was acquired and used as back up data but was not
employed in the calculation of the raw waste load. This
data was too random and had not been validated by on-site
sampling. However, the 200 plant survey summary was useful
in identifying current methods of in-plant treatment such as
silver recovery, bleach regeneration, bleach-fixer
regeneration, squeegees, and wash water controls which are
in-plant controls widely used in the industry. Further
information on these in-plant control measures was provided
by the EPOS Data Center in Sioux Falls, South Dakota. In
addition, a field visit to the Naval Photographic Center in
Washington, D.C. was made to develop an overview of
photographic processing technology in the military sector.
19
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SECTION IV
INDUSTRIAL CATEGORIZATION
General
The purpose of the total study is the development of
effluent limitations, guidelines and new source performance
standards for the photographic processing point source
category that will be commensurate with different levels of
in-process waste reduction and end-of-pipe pollution control
technology. "These effluent limitations and guidelines
specify the quantity of pollutants which will be discharged
from a specific facility and will be related to a common
yardstick for the manufacturing segment, such as quantity of
production.
Photographic Processing
Discussion of the Rationale of Categorization
The photographic processing subcategory serves the
photographic trade, the military establishment, the
scientific community, the medical profession, the dental
profession, and general public in the developing of films
and in photoprinting and enlarging. The following factors
were considered to determine whether further subdivision of
the subcategory and the establishment of separate effluent
limitations and guidelines for different point sources of
the subcategory were justified.
Plant Type
Photographic processing laboratories differ in the services
they provide. Among the estimated 12,500 processing plants
in the United States, approximately 3,000 are amateur
operations, 3,000 are "captive" laboratories in business and
industrial firms, 650 are major labs specializing in work
for professional and industrial photographers, and the
remaining plants are portrait and commercial studios. Table
IV-3 presents the FWL data summary for 30 non-Kodak plants
and 6 Kodak plants according to. NAPM's classification by
source of business. Based on this inspection, further
subdivision based on plant type was not justified.
Plant Size
Photoprocessing laboratories range in size from the small
amateur operations to the major professional laboratory
21
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which may process as much as 100,000 square feet of film and
paper daily. According to the NAPM many photographic
processing plants process between 25,000 and 50,000 square
feet per day. A profile of estimated plant sizes derived
from the 200 plant survey is given in Table IV-1. A
separate economic study was performed to determine the
economic impact of the recommended effluent limitations
reported in this text. This review indicated that the
Agency should incorporate a size cut-off and exempt
photographic processing plants which process less than 150
square meters per day (equivalent to 1,600 square feet per
day) .
Plant Location
Plants are located mostly in urban areas throughout the
country. The three plants for which RWL data were analyzed
were located in Michigan, Massachusetts, and Texas. In
addition a pilot biological treatment system was visited at
a plant in New York. Supplemental data (questionnaire)
compiled by Eastman Kodak Company for approximately 200
photographic processing plants was reviewed. During the
spring of 1976 NAPM took field samples from thirty plants
located in four U.S. metropolitan areas (New York,
Washington, D.C., Chicago and Detroit). In addition data
from six Eastman Kodak plants have been reviewed. Because
all plants operate within buildings and because the
processes require strict ambient processing conditions plant
location is not a basis for subcategorization.
Products
The products produced by the industry are finished color and
black and white films and prints of both. Most large plants
process both color and black and white materials; however,
one plant visited processed only color films and no
significant differences in the raw waste loadings were
observed. Difference in photographic products were
therefore, deemed not to be a basis for subcategorization.
Plant Processes
There are a wide variety of photoprocessing machines used to
finish a specific film or paper. These may be either the
continuous or "rack and tank" or "dip and dunk" operations.
The nature, basic principles and waste characteristics of
photograhic processing are the same in all facilities
regardless of size and age. Only the quantity of waste per
unit of production (Ibs per 1,000 square feet or kg per
1,000 square meters) showed a consistent relationship.
22
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TABLE IV -1
Plant Size From "200" Plant Survey Summary Data
*Wastewater Number of **Est. Production
gpd Plants sq. ft./day
less than 1,000 27 below 250
1,000 to 10,000 92 250 to 2,500
10,000 to 50,000 64 2,500 to 12,500
over 50,000 28 over 12,500
unknown 26
Total 237
*Wastewater flow profile from Table VII G-l
**Based on 4,000 gal/1,000 sq. ft. from Table VG-1
23
6/30/76
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Hence, process was
subcategorization.
eliminated as
basis
for
Wastewater Characteristics
As a result of the production of both color and black and
white products, large volumes of wastewater are discharged
during the process. These process wastewaters include both
photoprocessing solution overflows and wash waters.
Together, these spent waters are high in BOD, COD, TOC, TDS,
silver, and complex cyanide ion. Generally, the pollutants
of significance are the same for both color and black and
white photofinishing operations with the exception of
ferrocyanide, which is generated during the bleaching step
in color development. Therefore wastewater characteristics
are not a basis for subcategorization.
Summary of Considerations
Data was collected on both color and black and white
processes at three different plants identified as plants 32,
33, and 34. These plants varied in size by production, flow
rate, and geographic location, as shown in the following
tabulation:
Plant No.
(Location)
32 (Mich.)
33 (Mass.)
34 (Texas)
Average Daily
Production
sq ft
19,300
22,400
13,300
Flow Rate
gpd
62,600
67,900
42,000
Average Flow
gal/1000 sq.ft.
3,244
3,031
3,158
Based on the total quantity of production, measured in
square feet of product, pollutant loadings from the color
and black and white processes compare well in order-of-
magnitude. The arithmetic mean flow for the three plants of
3,144 gallons per 1,000 square feet of production covers all
three plants within a range of plus or minus 4 percent.
When the NAPM field survey for 30 non-Kodak plants is
combined with historical data for 6 Kodak plants, a weighted
flow of 4,050 gallons per 1000 square feet results. This is
reported in Table V-1 as plant number 00. The overall
industry RWL flow is computed by merging the 4 EPA
contractor data points together with the data points from
the 36 plants in the NAPM survey. The final overall RWL
flow rate is 4,000 gallons per 1000 per square feet. The
raw waste loads are fairly uniform throughout the industry
in color and black and white operations because of the
standardization of processes within the subcategory.
24
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Because of this uniformity, further division of the
subcategory for the. development of effluent limitations,
guidelines and new source performance standards could not be
justified on the basis of size, location, type of processing
or wastewater characteristics. The photographic processing
subcategory is treated as a whole for the purposes of this
document, and any analyses and regulations which are
developed will be applicable to the whole point source
category. Separate discussions of process types have,
however, been presented for a more thorough understanding of
the industry.
Process Descriptions
Most commercial photoprocessors handle many square feet of
film and paper with automatic processing machines. The
basic machines are called the "dip and dunk" or "rack and
tank" types, which consist of a series of tanks with each
tank containing photoprocessing solutions. These solutions
impart the desired effect on the film or paper in each
progressive step of development. Continuous length
processors are used by most large firms, and roller
transports are used in graphic arts and for hospital x-ray
films.
During photoprocessing, many changes occur within the
processing solutions. Because of these changes, the
chemicals used in photoprocessing need to be replaced,
strengthened, or replenished. Developing agents become
oxidized and exhausted; developer activators and
preservatives wear out; anti-foggants become used up;
bromides or other halides resulting from the reduction of
the silver by the developer become more concentrated; acid
short stops become neutralized; and the removal of silver
from the emulsion causes increased concentrations of silver
in the fixers or hypo baths. Chemicals are added to
maintain the correct chemical strength and photographic pro-
perties. When a replenisher is added, its volume must be
sufficient to cause enough overflow of the unwanted by-
products. Overflows from the processing tanks caused by the
addition of replenishers and wash water overflows are two
sources of wastewater from photoprocessing. Additional
process wastewater results from "leader running" for quality
control tests, from machines in "stand by" mode where
machine is "certified" for quality control but not running
film, and from start-up or shut-down operations.
Miscellaneous factors including spills, quick dumps, mix
tank washdown, machine room washdown, etc., contribute the
total flow.
25
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Leader to Film Relationship
By definition, a continuous processing machine cannot be run
without a leader. This leader is used to keep the machine
continuously threaded and is run while film is still in
other parts of the machine. Since film is still being
processed while this leader is run, wash water is still
required. Typical situations requiring leader are:
1. Leader is required for every film run:
(a) While a photographic check and scratch test is
run to certify the machine and process as
satisfactory for customers' work
(b) To fill the machine when customers' work is
finished.
2. Leader is required for dual purpose machines:
(a) If a machine runs two widths of film, such as
110 and 35 mm, leader is required to change
sizes, and to change back again.
(b) If a machine runs two separate processes, such
as Super 8 Ektachrome or ECO/ME-U, leader is
run to clear the machine before it is
rearranged.
3. Leader is required for special situations:
(a) If the web is damaged, either through machine
malfunction or web defects, leader must be run
to clear customers' film from the machine. In
the case of real, or suspected, machine
malfunctions, good practice requires running
scratch test and photographic certification
before processing any more customers' product.
(b) Occasionally, chemical errors or contami-
nations occur. These require leader for
similar reasons as mechanical problems.
The amount of leader that must be run in connection with a
square foot of film is highly variable. For example, it
depends on:
1. The total process ("dry-to-dry") time.
26
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2. The amount of customers1 film run. Since each run
takes a fixed amount of leader, the leader/film
ratio varies with the length of the film run.
Length of film run in turn depends on the time of
year, overall size of the plant, pattern of
incoming work, and committments to dealers for
service time.
3. The type of process and/or machine as "-detailed in
Item 2 above.'
U. The capacity of the specific machine in square
feet/minute in relation to square feet processed.
All of the above are considered as part of the overall raw
wastewater loads in the field survey.
Black and White Film
General
Black and white film consists of a foundation layer, which
is coated with a light-sensitive emulsion, and an outer
protective layer. Silver salts, made up of positively-
charged silver ions and negatively-charged bromide ions are
among the chemicals contained in the emulsion. When radiant
energy from light strikes the crystal, a dislodged electron
from the bromide ion is captured by a silver ion to form
metallic silver. The metallic silver clusters together on
the film surface and a latent image is formed. This image
is made visible by a step in photoprocessing called
development. Two development processes are used in
industry: the two-step negative-positive process and the
one-step reversal process.
Negative-positive Process
The silver bromide crystals in the gelatin emulsion are
bathed in a chemical solution called a developer, which
causes the visible image to form. The developer solution
contains developing agents, activators, preservatives,
restrainers, anti-foggants, and water conditioners. In
general, the developing agents for black and white
photography are aromatic compounds (for example,
hydroquinone).
After the photographic material has been developed the
desired amount, the developing process must be stopped.
This is normally done by treatment in an acidic solution
27
-------
called a short stop, which neutralizes the basic activators
of the developer and conditions the emulsion for future
processing steps. Sometimes plain water is sufficient for a
stop bath. After stopping the action of the developer, the
unexposed and undeveloped silver must be removed from the
emulsion. This is done not only to make the image more
visible and the film more transparent, but to prevent the
remaining unused silver from eventually being reduced to
metallic silver by the action of light. There are a number
of solvent fixers, including sodium thiosulfate, ammonium
thiosulfate, and sodium thiocyanate. Following fixation,
photographic materials are washed and dried. The process
flow diagram for black and white film is shown in Figure IV-
1.
The quality of wastewaters from black and white film
development is relatively uniform throughout the industry
and is characterized by the presence of hydroquinone in the
developer waste; sulfites in the stop bath waste; and
acetates, sulfites, and a silver thiosulfate complex in the
fixer waste. Inorganic oxygen-demanding chemicals such as
thiosulfate and sulfite are major components of all
processing effluents and may contribute more than 50% of the
oxygen demand for some processing wastewaters. Other wastes
are generated during the processing. These pollutants,
however, vary in type and concentration depending upon which
photoprocessing operation is employed.
Once the black and white negative has been fully processed
and is allowed to dry, the negative is transferred to a
positive paper print by the black and white paper process.
The process begins by directing a controlled exposure of
light onto the negative, thereby creating a positive image
on the paper, which has an emulsion layer similar to black
and white film. The latent image formed is then developed,
using different chemicals from those used in the film
development process. Wastewaters from the paper processing
are similar in type to the wastewaters in the film
development process, although the concentrations are usually
higher.
Reversal Development
This is a method for obtaining a positive image on the same
film used for the original exposure. The exposed film is
first fully developed to a negative. The film is then
washed and the silver image removed by bathing in an acidic
permanganate or dichromate bleach bath. A clearing bath
(for example, bisulfite) is used to remove the bleaching
agent and reaction products. The film is then given a
28
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Figure IV -1
Black and White Film Processing
Flow
Developers
^ Development
Waste
Water
(overflow)
Short Stop
Ingredients
r— ~j
^ Short Stop
Waste
Water
(overflow)
Fixers Water Vent
1 1 f
1 1
^ r
L_
\
Wa
Wa-
(ove
X : •" IAI
]
r
ste W
ber W
rflow) (ov
ash ^ Dry
1 1
aste
ater
erf low)
6/30/76
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uniform controlled exposure of light, and is developed a
second time. As an alternative to the second exposure, a
highly fogging developer or nonselective reducer may be used
for the second development. The process continues as in
other black and white processes with a wash, fix, final
wash, and dry. Reversal development is often used in
processing amateur and 16-mm motion picture film.
Wastewaters in reversal processing are similar to other
black and white film processing wastes. The process flow
diagram for black and white reversal film is shown in Figure
IV-2. Negative removal is accomplished by the addition of
dichromate bleach. Chemicals very similar to those used in
the development of color products are used in the black and
white development.
Color Film
General
In black and white photographic materials, the emulsion is
sensitive to wavelengths of light up to visible blue light.
However, certain organic compounds can be included in the
emulsion to extend the wavelength sensitivity of the silver
grains. The silver grains then become latent images when
exposed to green or red light. Color film has three
separate light-sensitive layers which record an image of the
blue light components on one layer, the green light
components on another and the red light components on a
third layer.
Negative-Positive Development
Color developer agents are generally N, N-dialkyl-p-
phenylene-diamines whose reaction products react with a
group of organic molecules called couplers to form dyes.
The oxidized components of this special category of
developers form colored dyes in the film emulsion layers
with the incorporated color couplers. Frequently a stop
bath follows the color developer step. As in black and
white film processing, metallic silver is formed in color
film upon exposure to light. However, in color film
processing the silver image which is formed with the dye is
converted back to silver halide by reactions with one of
several complex iron compounds and a halide. Either
ferricyanide with sodium bromide or ferric ammonium
ethylenediamine tetracetic acid (ferric EDTA) with ammonium
bromide is commonly used. Continuing the procedure of re-
moving the unwanted silver image after the bleaching step,
the film is treated in a fixer or hypo-bath. The film is
then washed to remove residual processing chemicals and
30
-------
Figure IV -2
Reversal Black and White Film Processing
i
Film
U)
Pre-
Hardening
Bath
Neutralizing 1
Bath 1 *"
!
Fi rst
Develop-
er
Wash
1
Negative
Removal
•- — -•••• —
Exposure to
Light or
Chemical
Fogging Agent
*
Waste
Water
(overflow)
Waste
Water
(overflow)
Waste
Water
(overflow)
Waste
Water
(overflow)
Waste
Water
(overflow)
Waste
Water
(overflow)
Process with
Normal Black
and White
Processing
6/30/76
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dried. Films of this type include Kodacolor and Agfa CNS.
The process flow diagram for color film development is shown
in Figure IV-3.
Effluent wastewaters from color film development are also
relatively uniform in quality and are characterized by the
presence of benzyl alcohol, developing agents, sulfates,
sulfites, borate, and phosphate in the developer wastes;
acetates in the short stop bath waste; ferrocyanide or
ferric EDTA in the bleach waste; and acetates, sulfites, and
silver thiosulfate complex in the fixing bath waste. The
major pollutants which contribute to BOD are benzyl alcohol,
sulfites, acetates, and thiosulfate.
Many variations of this basic process exist. Some color
processes combine the bleach and fixing steps to give a
"blix," which performs both operations simultaneously.
After the film is dried, positive paper prints are made by
exposing light through the film onto color photographic
paper with three color-sensitive layers containing couplers.
Processing of the print is similar to that used in the
negative development.
Color Reversal Development
There are two different types of color reversal films and
their processings are slightly different. In one, the
compounds which form the color image are incorporated into
the emulsion layers at the time of manufacture. Most color
reversal films are of this type. The second type of color
reversal film has three black and white color-sensitive
layers. In this type of film the color couplers are
included in the color developer solutions.
In processing the first kind of color reversal film, after
the negative image is formed, the emulsion is washed and may
be treated in a hardening bath. The silver not used to form
the negative image in the three layers is made developable
either by light or chemical action, and a positive silver
image is formed by the action of a color developer. The
oxidized developer combines with the couplers in the three
layers to form the three dye images. This part of the
process is very similar to the processing of color negative
material, except that the image on the film is positive.
The remaining steps are much the same. Films of this type
include Ektachrome, Ansochrome, Agfachrome, and Fugichrome.
The process flow diagram for color reversal development with
incorporated couplers is shown in Figure IV-4.
32
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Figure IV -3
Color Negative Film Processing
Film
. fc__
in ^"
co
co
Color
Developers
T
Color
*•» m i ^
Development"*
t
Waste
Water
(overflow)
Stop
Agents
I
Short
_,
*~ Stop
i
Waste
Water
(overflow)
Bleaching
Agents
, T
j
I
^h i~i n i •
^ Bleaching
^
Waste
Water
(overflow)
Fixers
jr.
^ F t i ,
•^ rlX
t
Waste
Water
(overflow)
Water Vent
1 t
-nn^to. 1 t<-| ."• Ll
^^ wash
^ Dry
I
Waste
Water
(overflow)
Finished
Color Film
Out /
^^
6/30/76
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Figure IV -4
Color Reversal Processing
(Incorporated Couplers)
L .1 _J.
r
Exposure to Proceed
Film ' •*• Hardening f"^1 Wash " ~ ^"j Development
Light or ». with Normal
, , , Chemical , Color
| | | ! I Fogging Processing
t t t
Waste Waste Waste
Water Water Water
(overflow) (overflow) (overflow)
6/30/76
-------
The wastes in the reversal process are similar to the color
process wastes except for the addition of sulfate from the
reversal bleach process and acetate and sulfate from the
hardening bath. Sulfamic acid is used in some reversal
black and white processes but is not used in color reversal
processes.
Color reversal film without the incorporated couplers is
processed in a manner similar to those just described up to
the formation of the negative image in all three layers.
After this, all three layers in the emulsion are treated
separately. First, the red-sensitive layer is made
developable by exposure to red light through the base of the
film. The other two layers, which are not sensitive to red
light, are unaffected. The film is then treated with a
color developer that contains, among many other ingredients,
a soluble cyan dye coupler. As the color developer agent
reduces the silver and forms an image, the oxidized color
developer in the vicinity of the developed silver grains
forms a positive cyan dye (red) image.
After washing, the film is exposed from the top with blue
light forming a latent image in the top blue-sensitive
layer. A yellow filter layer protects the middle green-
sensitive layer. A second color developer, containing a
soluble yellow coupler, produces both a silver and yellow
positive dye image in the top layer.
After a wash, the film is either exposed to white light or
chemically fogged and a third color developer, containing a
magenta coupler, forms the final positive silver and magenta
colored dye image (green). In the film or paper, there are
three negative silver images, three positive silver images
and three colored dye images. The silver images are removed
as in the negative color process by bleaching and fixing,
washing and drying. Films of this type include Kodachrome
and GAF Moviechrome. The process flow diagram for color
reversal development with couplers in the developer is shown
in Figure IV-5.
Ferricvanide in Photographic Processing Wastes
Ferricyanide bleaches are found in color photographic
processing applications, where it has been used as a
standard bleaching agent for years. The function of the
bleach in the photographic process is to oxidize the
metallic silver in the photographic emulsion to a silver
halide. During that oxidation, the ferricyanide and halide
ion concentrations of the bath decrease, while the
ferrocyanide concentration increases. Bromide ion is the
35
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FIGURE IV -5
COLOR REVERSAL PROCESSING (COUPLERS IN DEVELOPER)
FILM
DEVELOPMENT
1 A/ A C Ul
EXPOSE TO
RED LIGHT
DEVELOPMENT
WITH
CYAN COUPLER
TiTA CIJ
WAorl
EXPOST TO
BLUE LIGHT
DEVELOPMENT
WITH
YELLOW COUPLER
I
WASTE
WASTE
WASTE
WASTE
T
WASTE
WASH
I
EXPOSURE TO
WHITE LIGHT
OR CHEMICAL
FOGGING AGENT
WASTE
DEVELOPMENT
WITH
MAGENTA
COUPLER
BLEACH
FIX
WAon
DRY
WASTE
WASTE
WASTE
6/30/76
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Figure IV -6
Typical Photographic Processing
Flow Diagram
H W
MQ
i\\
w
LEGEND
H - Hardner
MQ - 1st Developer
C - Cyan
Y - Yellow
R - Reversal
M - Magenta
B - Bleach
F - Hypo Fix
W - Wash
W
T
W i R
Coupler
Recovery
Ifer
Couprer for
Reuse
Bleach
Regeneration
Silver
Recovery
Silver
Combined Process
Wastewater to
Treatment
37
W , M i W i W , B • F ! W ! W
arm
6/30/76
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most common halide ion. The reaction for photographic
bleaching is:
Ag° •*• Fe(CN)^-3 * Br- = AgBr + Fe(CN)e>~*
metallic ferri- Bromine Silver ferro-
silver cyanide ion Bromide cyanide
precipitate
To maintain the proper concentration of solution
constituents, the solution is constantly replenished with
fresh material. That distinguishes the two primary
solutions for all processing formulations, the replenisher
and working tank solutions. Table IV- 2 shows some typical
chemical concentrations for a working tank and a replenisher
tank from three different color photographic processes.
The overflow bleach from the working tank is one source of
ferrocyanide loss from the photographic process. In
addition, as film passes through the processing solutions,
it carries a certain volume of tank solution to the next
tank. That carryover is the total of the surface liquid and
the solution absorbed into the film emulsion. The carryover
rate depends upon many factors, including the speed of the
process and the photo products being processed. The
carryover loss of solution bleach into the next bath in the
process is a second source of bleach loss. The bath
following the bleach is either a photographic fixing bath or
a wash water.
All photographic processing laboratories are in a position
to estimate the average concentration of ferricyanide
discharged from the photographic laboratory over a specified
period of time. That can be done by calculating the pounds
of ferro- or ferricyanide purchased and dividing by the
total volume of water used by the laboratory during the same
period.
38
-------
TABLE IV -2
Bleach Bath Composition
EXAMPLE A - From a Typical Color Reversal Process
Working Tank Replenisher
(g/D (8/D
Sodium Ferrocyanide
(Na4Fe (CN)6- 10 H20) 45.0 5.0
Sodium Ferricyanide
(Na3Fe(CN)6) 120.0 140.0
Sodium Bromide
(NaBr) 25.0 55.0
EXAMPLE B - From A typical Color Negative Film Processor
Working Tank Replenisher
(g/D (g/D
Sodium Ferrocyanide
Decahydrate 6.0 2.0
Sodium Ferricyanide 23.0 26.0
Sodium Bromide 15.0 17.0
EXAMPLE C - From a Typical Color Positive Paper Processor
Working Tank Replenisher
(g/D (g/D
Sodium Ferrocyanide
Decahydrate 13.0 2.0
Sodium Ferricyanide 17.0 25.0
Sodium Bromide 7.0 8.0
39
6/30/76
-------
TABLE IV-3
STATISTICAL ANALYSIS OF NAPM/FIELD SURVEY - SPRING 1976
O
Type of
Operation
I
(Kodak Historical
Data)
I*
II
III
IV
Total Survey
Data
Statistical BOD
Parameter (lbs/1000 ft2)
Mean
Standard Deviation
Mean
Standard Deviation
Mean
Standard Deviation
Mean
Standard Deviation
Mean
Standard Deviation
Mean
Standard Deviation
12.09
9.40
4.84
2.51
4.41
2.02
4.64
2.68
11.58
12.59
7.5**
7.9
COD
(lbs/1000 ft^)
34.16
27.89
13.31
5.47
10.99
5.18
15.18
7.44
33.23
57.02
25
34
Flow
(gal/1000 f
6,279
3,070
2,857
2,209
3,365
1,417
4,428
2,720
3,584
3,327
4,050*
2,800
*Samples from plants number 12 and 16 were not included.
**Samples from plant number 16 was not included.
KEY: I = Amateur Photofinishers
II = Professional and Commercial Finishers
III = Does both I and II
IV = Motion Picture
6/30/76
-------
SECTION V
WASTE CHARACTERIZATION
The raw waste loadings (RWL) for the photoprocessing
industry presented in Table V-1 were determined from
analyses of samples collected during plant visits by the EPA
contractor and by NAPM. These data formed the data base and
generally were consistent with existing plant data. The EPA
contractor RWL in each case represents an average of four
values: one each from two black and white film and paper
operations and two color film and paper operations. The
pollutant loadings from these four operations compared well
in order-of-magnitude, and this formed the basis of
categorization. Final overall RWL's overflow, BOD^ and COD
are based on a weighted composite of data points from the 4
plants surveyed by the EPA contractor, from 30 non-Kodak
plants sampled by NAPM and from historical data from 6 Kodak
plants. The overall industry RWL flow is 4,000 gallons per
1000 square feet; the overall industry RWL, BOD5_ is 7.50 Ibs
per 1000 square feet and the overall industry RWL, COD is
25.1 Ibs per 1000 square feet. Supplemental information in
the form of calculated RWLs for typical photographic
processes is shown in Table V-2. The field survey revealed
no full scale secondary treatment plant installations for
stand alone photographic processing plants. The west coast
plant was used to confirm historical and field survey data.
The TSS data gathered from the field visits appeared to be
low in relation to the west coast plant and was considered
non-representative. The TSS RWL was, therefore, developed
from the west coast plant data.
Concentrations of the various parameters were determined
from grab samples collected from the combined wastewater
overflows and wash waters from each process (C-22, C-41, C-
42, Ektaprint 3, etc.). The concentration values for a
specific pollutant were found to vary among seemingly
identical machines. Because of this variation direct
comparison of the concentrations was not possible.
The constituents of the wastewater for which RWL were
determined were those parameters which are frequently
present in the wastewater and may have significant
ecological consequences once discharged. Other parameters
which may be potentially toxic to municipal treatment
plants, such as cadmium and chromium were generally found in
trace quantities.
41
-------
Table V -1
Raw Waste loads
Photographic Prb< e'S*-' ing Industry
Type of
Plant No. Operation
, BODr
32 Black & White 18.4
(3.77)
33 Black & White 41.6
(8.5)
32 Color 45.7
(9.34)
33 Color 1.46
(0.30)
34 Color 40.3
8.25
OO6 36.7
(7.5)
Paw Waste Load 36. 7
(7.5)'
RWL- Concentration, 225
Raw Waste Loa< -
COD
86.6
(17.7)
167.7
(34.3)
152.6
(31.2)
3.42
(0.7)
120.3
(24.6)
122
(25)
123.0
(25.1)'
752
TQC
11.1
(2.27)
48.9
(10.0)
34.2
(7.0)
1.12
(0.23)
44.1
(9.01)
N/A7
34.6
(7.07)'
212
TDS
319.8
(65.2)
307.1
(62.8)
158.9
(32.5)
31.5
(6.46)
219.0
(44.8)
N/A7
251.0
(51.3)'
1,538
Silver
0.10
(0.02 )
0.08
(0.016)
0.06
(0.013)
0.05
(0.011)
0.08
(0.016)
N/A7
0.07
(0.015?
0.45
TSS
1.
(3.
0.
(0.
J f
(0.
0.
(0.
0.
Phenol
48 x 10" u
03 x 10-5;
0097
0020)
0078
0016)
029
0059)
Oil
(0.0023)
N/A7
3.03 0.014
(0.622JV..003 )2
19 0.
09
kg/1 ,000 sq. IT.. (Ibs./I ,000
1 ron
0.10
(0.021)
10.4
(2.14)
0.85
(0.174)
0.25
(0.0509)
0.69
(0.142)
N/A7
2.47
(0.506)
15.2
Boron
7.03
(1.44)
0.01
(0.0021)
0.75
(0.154)
0.07
(0.0142)
0.73
(0.15)
/A7
2.15
(0.44 )3
13.2
T-P
0.13
(0.027)
0.36
(0.074)
0.18
(0.036)
0.69
(0.141)
1.17
(0.24)
N/A7
0.507
(0.104)
3.1
sq. ft.)
Surfactants
0.33
(0.0679)
0.07
(0.0144)
o.ou
(0.0215)
N/A7
0.17
(0.035)
1.1
TKN
4.9
(1.005)
46.0
(9.42)
13.4
(2.75)
1.19
(0.243)
3.98
(0.814)
N/A7
13.9
(2.85)
85
Total Cyanide
0.09
(0.019)
0.57 8
mg/t/*
Plant 33 - Color not included in RWL average
Plant 32 - Black and White not included in RWL average
Plant 33 - Black and White not included in RWL average
Values based on average wastewater flow from the three plants (4,000 i?l|ons per 1,000 sq. ft.)-except for TSS, total cyanide, and ferrocyanide
Values based on data obtained from Eastman Kodak's Palo Alto Plant
^Val'jss fron 73 additional data points from 36 plants.
7 N/A = not available.
8 Value based on average from 55 parameter analysis results and used -riA *,VQC gal./1,000 sq. ft. flow rate to back calculate
Raw Waste load mass loadings per area irrmedaately above.
6/30/76
-------
TABLE V -2
Calculated RWL for Typical Photographic Processes
Flow BODS
gal/1000 sq. ft. Ib/lOOOsq. ft.
COD
Ib/lOOOsq. ft.
RWL
Ektaprint 31 - 4C - 2K
Processor 15' /min
2-3-1/2" strands
Kodachrome K-142>3 -
at 50 '/min
Ektachrome EA-5 - 9-1/2"
at 3.2 '/min 1411-M
Ektachrome E-4 35mm at
26 '/min
Ektaprint R-5 - 3-1/2" at
3 '/min 4R Processor
Eastman Color Print
- 35 mm at 125 '/min
Eastman Color Negative
- 35 mm at 50 '/min
B$W Paper - 5" at 6.66
'/min Himatic Chemicals
B§W Aerial Film - 5" at
14 '/min Versamat 641
Dev. § Fix
DuPont Graphic Arts Process
DuPont Medical X-Ray
Processing
Cronaflex^Engineering
Reproduction
2960
542
3015
2660
4420
t 12000
1280
1470
1460
195
ess
7.36
5.42
6.1
62.
43.5
26.7
23.2
26.4
4.5
6
35
17
26.
9.
21
95
67.
44.
30
37.
5.
8
51
21
4
8
5
8
3
4
11.5
14
Bl-Fix Regeneration
2% 1-Re generation
Fixer Regeneration
Data Supplied by NAPM
43
6/30/76
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
General
From review of NPDES permit applications for direct
discharge of wastewaters from the photographic processing
subcategory of the photographic point source category and
examination of related published data, twenty parameters
(listed in Table VI- 1) were selected and examined during the
field data collection program. All field sampling data are
summarized in Supplement B. Supplement B includes
laboratory analytical results, data from plants visited, RWL
calculations, historical data, analysis of historical data,
computer print-outs (showing flows, production, and
pollutants, performance data on treatment technologies and
effluent limitations calculations) . Supplement B is
available for examination at the EPA Public Information
Reference Unit, Room 2922, (EPA Library) , Waterside Mall,
M. St., S.W. , Washington, D.C. 20460.
The degree of impact on the overall environment has been
used as a basis for dividing the pollutants into groups as
follows:
Pollutants of significance.
Rationale for the selection of pollutant parameters.
Pollutants of specific significance.
The rationale and justification for pollutant categorization
within the foregoing groupings, as discussed herein, will
indicate the basis for selection of the parameters upon
which the actual effluent limitations and guidelines were
postulated. In addition, particular parameters have been
discussed in terms of their validity as measures of
environmental impact.
Pollutants observed from photographic processing field data
that were present in sufficient concentrations so as to
interfere with, be incompatible with, or pass with
inadequate treatment through publicly owned treatment works
are discussed in Section XII of this document.
Pollutants of Significance
45
-------
Parameters of major concern are BODJ5, COD, silver and
cyanides in various .forms including complexes (ferrocyanide
and ferric cyanide).
BOD5 and ' COD have been selected as pollutants of
significance because they are the primary measurements of
organic pollution. In the survey of the industrial
categories, most of the effluent data collected from
wastewater treatment facilities were based upon BOD5,
because most of the end-of-pipe treatment facilities and
municipal treatment systems were biological processes.
Where other processes (such as evaporation, incineration,
activated carbon or physical/chemical) are utilized, either
COD or TOC may be a more appropriate measure of pollution.
46
-------
Table VI-1
List of Parameters to be Examined
Acidity and Alkalinity-pH
Dissolved Oxygen
Biochemical Oxygen Demand
Chemical Oxygen Demand
Total Organic Carbon
Total Suspended Solids
Phenol
Phosphorus
Dissolved Solids
Nitrogen Compounds
Sulfates
Temperature
Boron
Cadmium
Chromium
Cyanide
Ferrocyanide
Silver
Thiosulfate
Dye Couplers
47
-------
RATIONALE FOR THE SELECTION OF POLLUTANT PARAMETERS
I. Pollutant Properties
Acidity and Alkalinity - pH
Although not a specific pollutant, pH is related to the
acidity or alkalinity of a waste water stream. It is not a
linear or direct measure of either, however, it may properly
be used as a surrogate to control both excess acidity and
excess alkalinity in water. The term pH is used to describe
the hydrogen ion - hydroxyl ion balance in water.
Technically, pH is the hydrogen ion concentration or
activity present in a given solution. pH numbers are the
negative logarithm of the hydrogen ion concentration. A pH
of 7 generally indicates neutrality or a balance between
free hydrogen and free hydroxyl ions. Solutions with a pH
above 7 indicate that the solution is alkaline, while a pH
below 7 indicates that the solution is acid.
Knowledge of the pH of water or waste water is useful in
determining necessary measures for corrosion control,
pollution control, and disinfection. Waters with a pH below
6.0 are corrosive to water works structures, distribution
lines, and household plumbing fixtures and such corrosion
can add constituents to drinking water such as iron,
copper, zinc, cadmium, and lead. Low pH waters not only
tend to dissolve metals from structures and fixtures but
also tend to redissolve or leach metals from sludges and
bottom sediments. The hydrogen ion concentration can affect
the "taste" of the water and at a low pH, water tastes
"sour".
Extremes of pH or rapid pH changes can exert stress
conditions or kill aquatic life outright. Even moderate
changes from "acceptable" criteria limits of pH are
deleterious to some species. The relative toxicity* to
aquatic life of many materials is increased by changes in
the water pH. For example, metalocyanide complexes can
increase a thousand-fold in toxicity with a drop of 1.5 pH
units. Similarly, the toxicity of ammonia is a function of
pH. The bactericidal effect of chlorine in most cases is
less as the pH increases, and it is economically
advantageous to keep the pH close to 7.
*The term toxic or toxicity is used herein in the normal
scientific sense of the word and not as a specialized
term referring to section 307 (a) of the Act.
48
-------
Acidi-ty is defined as the quantitative ability of a water to
neutralize hydroxyl ions. It is usually expressed as the
calcium carbonate equivalent of the hydroxyl ions
neutralized. Acidity should not be confused with pH value.
Acidity is the quantity of hydrogen ions which may be
released to react with or neutralize hydroxyl ions while pH
is a measure of the free hydrogen ions in a solution at the
instant the pH measurement is made. A property of many
chemicals, called buffering, may hold hydrogen ions in a
solution from being in the free state and being measured as
pH. The bond of most buffers is rather weak and hydrogen
ions tend to be released from the buffer as needed to
maintain a fixed pH value.
Highly acid waters are corrosive to metals, concrete and
living organisms, exhibiting the pollutional characteristics
outlined above for low pH waters. Depending on buffering
capacity, water may have a higher total acidity at pH values
of 6.0 than other waters with a pH value of 4.0.
Alkalinity; Alkalinity is defined as the ability of a water
to neutralize hydrogen ions. It is usually expressed as the
calcium carbonate equivalent of the hydrogen ions
neutralized.
Alkalinity is commonly caused by the presence of carbonates,
bicarbonates, hydroxides and to a lesser extent by borates,
silicates, phophates and organic substances. Because of the
nature of the chemicals causing alkalinity, and the
buffering capacity of carbon dioxide in water, very high pH
values are seldom found in natural waters.
Excess alkalinity as exhibited in a high pH value may make
water corrosive to certain metals, detrimental to most
natural organic materials and toxic to living organisms.
Ammonia is more lethal with a higher pH. The lacrimal fluid
of the human eye has a pH of approximately 7.0 and a
deviation of 0.1 pH unit from the norm may result in eye
irritation for the swimmer. Appreciable irritation will
cause severe pain.
Oxygen Demand (BOD, COD, TOC and
Organic and some inorganic compounds can cause an oxygen
demand to be exerted in a receiving body of water.
Indigenous microorganisms utilize the organic wastes as an
energy source and oxidize the organic matter. In doing so
their natural respiratory activity will utilize the
dissolved oxygen.
49
-------
Dissolved oxygen (DO) in water is a quality that, in
appropriate concentrations, is essential not only to keep
organisms living but also to sustain species reproduction,
vigor, and the development of populations. Organisms
undergo stress at reduced DO concentrations that make them
less competitive and less able to sustain their species
within the aquatic environment. For example, reduced DO
concentrations have been shown to interfere with fish
population through delayed hatching of eggs, reduced size
and vigor of embryos, production of deformities in young,
interference with food digestion, acceleration of blood
clotting, decreased tolerance to certain toxicants, reduced
food utilization efficiency, growth rate, and maximum
sustained swimming speed. Other organisms are likewise
affected adversely during conditions of decreased DO. Since
all aerobic aquatic organisms need a certain amount of
oxygen, the consequences of total depletion of dissolved
oxygen due to a high oxygen demand can kill all the
inhabitants of the affected aquatic area.
It has been shown that fish may, under some natural
conditions, become acclimatized to low oxygen
concentrations. Within certain limits, fish can adjust
their rate of respiration to compensate for changes in the
concentration of dissolved oxygen. It is generally agreed,
moreover, that those species which are sluggish in movement
(e.g.,carp, pike, eel) can withstand lower oxygen
concentrations than fish which are more lively in habit
(such as trout or salmon) .
The lethal affect of low concentrations of dissolved oxygen
in water appears to be increased by the presence of toxic
substances, such as ammonia, cyanides, zinc, lead, copper,
or cresols. With so many factors influencing the effect of
oxygen deficiency, it is difficult to estimate the minimum
safe concentrations at which fish will be unharmed under
natural conditions. Many investigations seem to indicate
that a DO level of 5.0 mg/1 is desirable for a good aquatic
environment and higher DO levels are required for selected
types of aquatic environments.
Biochemical oxygen demand (BOD) is the quantity of oxygen
required for the biological and chemical oxidation of
waterborn substances under ambient or test conditions.
Materials which may contribute to the BOD include:
carbonaceous organic materials usable as a food source by
aerobic organisms; oxidizable nitrogen derived from
nitrites, ammonia and organic nitrogen compounds which serve
as food for specific bacteria; and certain chemically
oxidizable materials such as ferrous iron, sulfides.
50
-------
sulfite, etc. which will react with dissolved oxygen or are
metabolized by bacteria. In most industrial and municipal
waste waters, the BOD derives principally from organic
materials and from ammonia (which is itself derived from
animal or vegetable matter) .
The BOD of a waste exerts an adverse effect upon the
dissolved oxygen resources of a body of water by reducing
the oxygen available to fish, plant life, and other aquatic
species. Conditions can be reached where all of the
dissolved oxygen in the water is utilized resulting in
anaerobic conditions and the production of undesirable gases
such as hydrogen sulfide and methane. The reduction of
dissolved oxygen can be detrimental to fish populations,
fish growth rate, and organisms used as fish food. A total
lack of oxygen due to the exertion of an excessive BOD can
result in the death of all aerobic aquatic inhabitants in
the affected area.
Water with a high BOD indicates the presence of decomposing
organic matter and associated increased bacterial
concentrations that degrade its quality and potential uses.
A by-product of high BOD concentrations can be increased
algal concentrations and blooms which result from
decomposition of the organic matter and which form the basis
of algal populations.
The BODJ5 (5-day BOD) test is used widely to estimate the
pollutional strength of domestic and industrial wastes in
terms of the oxygen that they will require if discharged
into receiving streams. The test is an important one in
water pollution control activities. It is used for
pollution control regulatory activities, to evaluate the
design and efficiencies of waste water treatment works, and
to indicate the state of purification or pollution of
receiving bodies of water.
Complete biochemical oxidation of a given waste may require
a period of incubation too long for practical analytical
test purposes. For this reason, the 5-day period has been
accepted as standard, and the test results have been
designated as BODJ5. Specific chemical test methods are not
readily available for measuring the quantity of many
degradable substances and their reaction products. Reliance
in such cases is placed on the collective parameter, BOD5_,
which measures the weight of dissolved oxygen utilized by
microorganisms as they oxidize or transform the gross
mixture of chemical compounds in the waste water. The
biochemical reactions involved in the oxidation of carbon
compounds are related to the period of incubation. The
51
-------
five-day BOD normally measures only 60 to 8056 of the
carbonaceous biochemical oxygen demand of the sample, and
for many purposes this is a reasonable parameter.
Additionally, it can be used to estimate the gross quantity
of oxidizable" organic matter.
The BODji test is essentially a bioassay procedure which
provides an estimate of the oxygen consumed by
microorganisms utilizing the degradable matter present in a
waste under conditions that are representative of those that
are likely to occur in nature. Standard conditions of time,
temperature, suggested microbial seed, and dilution water
for the wastes have been defined and are incorporated in the
standard analytical procedure. Through the use of this
procedure, the oxygen demand of diverse wastes can be
compared and evaluated for pollution potential and to some
extent for treatability by biological treatment processes.
Because the BOD test is a bioassay procedure, it is
important that the environmental conditions of the test be
suitable for the microorganisms to function in an
uninhibited manner at all times. This means that toxic
substances must be absent and that the necessary nutrients,
such as nitrogen, phosphorous, and trace elements, must be
present.
Chemical oxygen demand (COD) is a purely chemical oxidation
test devised as an alternate method of estimating the total
oxygen demand of a waste water. Since the method relies on
the oxidation-reduction system of chemical analyses rather
than on biological factors, it is more precise, accurate,
and rapid than the BOD test. The COD test is widely used to
estimate the total oxygen demand (ultimate rather than 5-day
BOD) to oxidize the compounds in a waste water. It is based
on the fact that organic compounds, with a few exceptions,
can be oxidized by strong chemical oxidizing agents under
acid conditions with the assistance of certain inorganic
catalysts.
The COD test measures the oxygen demand of compounds that
are biologically degradable and of many that are not.
Pollutants which are measured by the BODS^ test will be
measured by the COD test. In addition, pollutants which are
more resistant to biological oxidation will also be measured
as COD. COD is a more inclusive measure of oxygen demand
than is BODJ5 and will result in higher oxygen demand values
than will the BODj> test.
The compounds which are more resistant to biological
oxidation are becoming of greater and greater concern not
52
-------
only because of their slow but continuing oxygen demand on
the resources of the receiving water, but also because of
their potential health effects on aquatic life and humans.
Many of these compounds result from industrial discharges
and some have been found to have carcinogenic, mutagenic and
similar adverse effects, either singly or in combination.
Concern about these compounds has increased as a result of
demonstrations that their long life in receiving waters -
the result of a slow biochemical oxidation rate - allows
them to contaminate downstream water intakes. The commonly
used systems of water purification are not effective in
removing these types of materials and disinfection such as
chlorination may convert them into even more hazardous
materials.
Thus the COD test measures organic matter which exerts an
oxygen demand and which may affect the health of the people.
It is a useful analytical tool for pollution control
activities. It provides a more rapid measurement of the
oxygen demand and an estimate of organic compounds which are
not measured in the BOD5 test.
Total organic carbon JTOC)^ is measured by the catalytic
conversion of organic carbon in a waste water to carbon
dioxide. Most organic chemicals have been found to be
measured quantitatively by the equipment now in use. The
time of analyses is short, from 5 to 10 minutes, permitting
a rapid and accurate estimate of the organic carbon content
of the waste waters to be made by relatively unskilled
personnel.
A TOC value does not indicate the rate at which the carbon
compounds are oxidized in the natural environment. The TOC
test will measure compounds that are readily biodegradable
and measured by the BOD5 test as well as those that are not.
TOC analyses will include those biologically resistant
organic compounds that are of concern in the environment.
BOD and COD methods of analyses are based on oxygen
utilization of the waste water. The TOC analyses estimates
the total carbon content of a waste water. There is as yet
no fundamental correlation of TOC to either BOD or COD.
However, where organic laden waste waters are fairly
uniform, there will be a fairly constant correlation among
TOC, BOD and COD. Once such a correlation is established,
TOC can be used as an inexpensive test for routine process
monitoring.
53
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Total Suspended Solids (TSS)
Suspended solids include both organic and inorganic
materials. The inorganic compounds include sand, silt, and
clay. The organic fraction includes such materials as
grease, oil, tar, and animal and vegetable waste, products.
These solids may settle out rapidly and bottom deposits are
often^a mixture- of both organic and inorganic solids.
Solids may be suspended in water for a time, and then settle
to the bed of the stream or lake. These solids discharged
with man's wastes may be inert, slowly biodegradable
materials, or rapidly decomposable substances. While in
suspension, they increase the turbidity of the water, reduce
light penetration and impair the photosynthetic activity of
aquatic plants.
Suspended solids in water interfere with many industrial
processes, cause foaming in boilers and incrustations on
equipment exposed to such water, especially as the
temperature rises. They are undesirable in process water
used in the manufacture of steel, in the textile industry,
in laundries, in dyeing, and in cooling systems.
Solids in suspension are aesthetically displeasing. When
they settle to form sludge deposits on the stream or lake
bed, they are often damaging to the life in water. Solids,
when transformed to sludge deposits, may do a variety of
damaging things, including blanketing the stream or lake bed
and thereby destroying the living spaces for those benthic
organisms that would otherwise occupy the habitat. When of
an organic nature, solids use a portion or all of the
dissolved oxygen available in the area. Organic materials
also serve as a food source for sludgeworms and associated
organisms.
Disregarding any toxic effect attributable to substances
leached out by water, suspended solids may kill fish and
shellfish by causing abrasive injuries and by clogging the
gills and respiratory passages of various aquatic fauna.
Indirectly, suspended solids are inimical to aquatic life
because they screen out light, and they promote and maintain
the development of noxious conditions through oxygen
depletion. This results in the killing of fish and fish
food organisms. Suspended solids also reduce the
recreational value of the water.
Turbidity: Turbidity of water is related to the amount of
suspended and colloidal matter contained in the water. It
affects the clearness and penetration of light. The degree
of turbidity is only an expression of one effect of
54
-------
suspended solids upon the character of the water. Turbidity
can reduce the effectiveness of chlorination and can result
in difficulties in meeting BOD and suspended solids
limitations. Turbidity is an indirect measure of suspended
solids.
Phenols
Phenols, defined as hydroxy derivatives of benzene and its
condensed nuclei, may occur in domestic and industrial waste
water and in drinking water supplies. Chlorination of such
waters can produce odoriferous and objectionable tasting
chlorophenols which may include o-chlorophenol, p-
chlorophenol, and 2, U-dichlorophenol.
Although described in the technical literature simply as
phenols, the phenol waste category can include a wide range
of similar chemical compounds. In terms of pollution
control, reported concentrations of phenols are the result
of a standard methodology which measures a general group of
similar compounds rather than being based upon specific
identification of the single compound, phenol
(hydroxybenzene) .
Phenols are used in some cutting oils and in the molding of
plastics. Cutting fluids can contain phenolic compounds
since these materials are normal constituents of hydrocarbon
mixtures. In addition, phenolic compounds are added to oils
as preservatives or for odor control. They also are found
in the waste waters from the petroleum industry and from
certain products of the organic chemical industry.
Phenolic compounds may adversely affect fish in two ways:
first, by a direct toxic action, and second, by imparting a
taste to the fish flesh. The toxicity of phenol towards
fish increases as the dissolved oxygen level is diminished,
as the temperature is raised, and as the hardness is
lessened. Phenol appears to act as a nerve poison causing
too much blood to get to the gills and to the heart cavity
and is reported to have a toxic threshold of 0.1 - 1.5 mg/1.
Mixed phenolic substances appear to be especially
troublesome in imparting taste to fish flesh. Chlorophenol
produces a bad taste in fish far below lethal or toxic
doses. Threshold concentrations for taste or odor in
chlorinated water supplies have been reported as low as
0.00001-0.001 mg/1. Phenols in concentrations of only one
part per billion have been known to affect water supplies.
55
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The ingestion of concentrated solutions of phenol by humans
results in severe pain, renal irritation, shock, and
possibly death. A total dose of 1.5 grams may be fatal.
Phenols can be metabolized and oxidized in waste treatment
facilities containing organisms acclimated to the phenol
concentration in the wastes.
Phosphorus
Phosphorus occurs in natural waters and in waste waters in
the form of various types of phosphate. These forms are
commonly classified into orthophosphat.es, condensed
phosphates (pyro-, meta-, and polyphosphorus), and
organically bound phosphates. These may occur in the
soluble form, in particles of detritus or in the bodies of
aquatic organisms.
The various forms of phosphates find their way into waste
waters from a variety of industrial, residential, and
commercial sources. Small amounts of certain condensed
phosphates are added to some water supplies in the course of
potable water treatment. Large quantities of the same
compounds may be added when the water is used for laundering
or other cleaning since these materials are major
constituents of many commercial cleaning preparations.
Phosphate coating of metals is another major source of
phosphates in certain industrial effluents.
The increasing problem of the growth of algae in streams and
lakes appears to be associated with the increasing presence
of certain dissolved nutrients, chief among which is
phosphorus. Phosphorus is an element which is essential to
the growth of organisms and it can often be the nutrient
that limits the aquatic growth that a body of water can
support. In instances where phosphorous is a growth
limiting nutrient, the discharge of sewage, agricultural
drainage or certain industrial wastes to a receiving water
may stimulate the growth, in nuisance quantities, of
photosynthetic aquatic microorganisms and macroorganisms.
The increase in organic matter production by algae and
plants in a lake undergoing eutrophication has ramifications
throughout the aquatic ecosystem. Greater demand is placed
on the dissolved oxygen in the water as the organic matter
decomposes at the termination of the life cycles. Because
of this process, the deeper waters of the lake may become
entirely depleted of oxygen, thereby, destroying fish
habitats and leading to the elimination of desirable
species. The settling of particulate matter from the
productive upper layers changes the character of the bottom
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mud, also leading to the replacement of certain species by
less desirable organisms. Of great importance is the fact
that nutrients inadvertently introduced to a lake are, for
the most part, trapped there and recycled in accelerated
biological processes. Consequently, the damage done to a
lake in a relatively short time requires a many fold in-
crease in time for recovery of the lake.
When a plant population is stimulated in production and
attains a nuisance status, a large number of associated
liabilities are immediately apparent. Dense populations of
pond weeds make swimming dangerous. Boating and water
skiing and sometimes fishing may be eliminated because of
the mass of vegetation that serves as a physical impediment
to such activities. Plant populations have been associated
with stunted fish populations and with poor fishing. Plant
nuisances emit vile stenches, impart tastes and odors to
water supplies, reduce the efficiency of industrial and
municipal water treatment, impair aesthetic beauty, reduce
or restrict resort trade, lower waterfront property values,
cause skin rashes to man during water contact, and serve as
a desired substrate and breeding ground for flies.
Phosphorus in the elemental form is particularly toxic, and
subject to bioaccumulation in much the same way as mercury.
Colloidal elemental phosphorus will poison marine fish
(causing skin tissue breakdown and discoloration). Also,
phosphorus is capable of being concentrated and will
accumulate in organs and soft tissues. Experiments have
shown that marine fish will concentrate phosphorus from
water containing as little as 1 ug/1.
Dissolved Solids
In natural waters, the dissolved solids are mainly
carbonates, chlorides, sulfates, phosphates, and, to a
lesser extent, nitrates of calcium, magnesium, sodium, and
potassium, with traces of iron, manganese and other
substances.
Many communities in the United States and in other countries
use water supplies containing 2,000 to U,000 mg/1 of
dissolved salts, when no better water is available. Such
waters are not palatable, may not quench thirst, and may
have a laxative action on new users. Waters containing more
than *»,000 mg/1 of total salts are generally considered
unfit for human use, although in hot climates such higher
salt concentrations can be tolerated. Waters containing
5,000 mg/1 or more are reported to be bitter and act as a
bladder and intestinal irritant. It is generally agreed
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that the salt concentration of good, palatable water should
not exceed 500 mg/1.
Limiting concentrations of dissolved solids for fresh-water
fish may range from 5,000 to 10,000 mg/1, depending on
species and prior acclimatization. Some fish are adapted to
living in more saline waters, and a few species of fresh-
water forms have been found in natural waters with a salt
concentration of 15,000 to 20,000 mg/1. Fish can slowly
become acclimatized to higher salinities, but fish in waters
of low salinity cannot survive sudden exposure to high
salinities, such as those resulting from discharges of oil-
well brines. Dissolved solids may influence the toxicity of
heavy metals and organic compounds to fish and other aquatic
life, primarily because of the antagonistic effect of
hardness on metals.
Waters with total dissolved solids (TDS) concentrations
higher than 500 mg/1 have decreasing utility as irrigation
water. At 5,000 mg/1, water has little or no value for
irrigation.
Dissolved solids in industrial waters can cause foaming in
boilers and can cause interference with cleanliness, color,
or taste of many finished products. High concentrations of
dissolved solids also tend to accelerate corrosion.
Specific conductance is a measure of the capacity of water
to convey an electric current. This property is related to
the total concentration of ionized substances in water and
to the water temperature. This property is frequently used
as a substitute method of quickly estimating the dissolved
solids concentration.
Nitrogen Compounds
Ammonia nitrogen (NH3-N) and total Kjeldahl nitrogen (TKN)
are two parameters which have received a substantial amount
of interest in the last decade. TKN is the sum of the NH^-N
and organic nitrogen present in the sample. Both NH3 and
TKN are expressed in terms of equivalent nitrogen values in
mg/1 to facilitate mathematical manipulations of the values.
Organic nitrogen may be converted in the environment to
ammonia by saprophytic bacteria under either aerobic or
anaerobic conditions. The ammonia nitrogen then becomes the
nitrogen and energy source for autotrophic organisms
(nitrifiers). The oxidation of ammonia to nitrite and then
to nitrate has a stoichiometric oxygen requirement of
approximately 4.6 times the concentration of NH_3-N. The
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nitrification reaction is much slower than the carbonaceous
reactions, and, therefore, the dissolved oxygen utilization
is observed over a much longer period.
Ammonia is a common product of the decomposition of organic
matter. Dead and decaying animals and plants along with
human and animal body wastes account for much of the ammonia
entering the aquatic ecosystem. Ammonia exists in its non-
ionized form only at higher pH levels and is the most toxic
in this state. The lower the pH, the more ionized ammonia
is formed and its toxicity decreases. Ammonia, in the
presence of dissolved oxygen, is converted to nitrate (NO^)
by nitrifying bacteria. Nitrite (NO£), which is an
intermediate product between ammonia and nitrate, sometimes
occurs in quantity when depressed oxygen conditions permit.
Ammonia can exist in several other chemical combinations,
including ammonium chloride and other salts.
Infant methemoglobinemia, a disease characterized by
specific blood changes and cyanosis, may be caused by high
nitrate concentrations in the water used for preparing
feeding formulae. While it is still impossible to state
precise concentration limits, it has been widely recommended
that water containing more than 10 mg/1 of nitrate nitrogen
(NOJ5-N) should not be used for infants.
Nitrates are also harmful in fermentation processes and can
cause disagreeable tastes in beer. In most natural water
the pH range is such that ammonium ions (NHU-*-) predominate.
In streams polluted with sewage, up to one-half of the
nitrogen in the sewage may be in the form of free ammonia,
and sewage may carry up to 35 mg/1 of total nitrogen. It
has been shown that at a level of 1.0 mg/1 non-ionized
ammonia, the ability of hemoglobin to combine with oxygen is
impaired and may cause fish to suffocate. Evidence
indicates that ammonia exerts a considerable toxic effect on
all aquatic life within a range of less than 1.0 to 25 mg/1,
depending on the pH and dissolved oxygen level present.
Ammonia can add to the problem of eutrophication by
supplying nitrogen through its breakdown products. some
lakes in warmer climates, and others that are aging quickly,
are sometimes limited by the nitrogen available. Any
increase will speed up the plant growth and decay process.
Sulfates
Sulfates occur naturally in waters, particulary in the
western Unites States, as a result of leachings from gypsum
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and other common materials. They also occur as the final
oxidized state of sulfides, sulfites and thiosulfates.
Sulfates may also be present as the oxidized state of
organic matter in the sulfur cycle, but they in turn, may
serve as sources of energy for sulfate splitting bacteria.
Sulfates may also be discharged in numerous industrial
wastes, such as those from tanneries, sulfate-pulp mills,
textile mills, and other plants that use sulfates or
sulfuric acid.
In moderate concentrations, sulfates are not harmful and it
has been reported that concentrations up to 1000 mg/1 are
harmless. Irrigation concentrations less than 336 mg/1 are
considered to be good to excellent.
Temperature
Temperature is one of the most important and influential
water quality characteristics. Temperature determines what
species may be present; it activates the hatching of young,
regulates their activity, and stimulates or suppresses their
growth and development; it attracts, and may kill when the
water becomes too hot or becomes chilled too suddenly.
Colder water generally suppresses development. Warmer water
generally accelerates activity and may be a primary cause of
aquatic plant nuisances when other environmental factors are
suitable.
Temperature is a prime regulator of natural processes within
the water environment. It governs physiological functions
in organisms and, acting directly or indirectly in
combination with other water quality constituents, affects
aquatic life with each change. These effects include
chemical reaction rates, enzymatic functions, molecular
movements, and molecular exchanges between membranes within
and between the physiological systems and the organs of an
animal.
Chemical reaction rates vary with temperature and generally
increase as the temperature is increased. The solubility of
gases in water varies with temperature. Dissolved oxygen is
decreased by the decay or decomposition of dissolved organic
substances, and the decay rate increases as the temperature
of the water increases, reaching a maximum at about 30°C
(86°F). The temperature of stream water, even during
summer, is below the optimum for pollution-associated
bacteria. Increasing the water temperature increases the
bacterial multiplication rate when the environment is
favorable and the food supply is abundant.
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Reproduction cycles may be changed significantly by
increased temperature because this function takes place
under restricted temperature ranges.
Spawning may not occur at all when temperatures are too
high. Thus, a fish population may exist in a heated area
only by continued immigration. Disregarding the decreased
reproductive potential, water temperatures need not reach
lethal levels to decimate a species. Temperatures that
favor competitors, predators, parasites, and disease can
destroy a species at levels far below those that are lethal.
Fish food organisms are altered severely when temperatures
approach or exceed 90°F. Predominant algal species change;
primary production is decreased; and bottom-associated
organisms may be depleted or altered drastically in numbers
and distribution. Increased water temperature may cause
aquatic plant nuisances when other environmental factors are
favorable.
Synergistic actions of pollutants are more severe at higher
water temperatures. Domestic sewage, refinery wastes, oils,
tars, insecticides, detergents, and fertilizers deplete
oxygen in water more rapidly at higher temperatures, and the
respective toxicities are likewise increased.
When water temperatures increase, the predominant algal
species may change from diatoms, to green algae, then, at
high temperatures, to blue-green algae because of species
temperature preferentials. Blue-green algae can cause
serious odor problems. The number and distribution of
benthic organisms decreases as water temperature increases
above 90°F, which is close to the tolerance limit for the
water's population. This could seriously affect certain
fish that depend on benthic organisms as a food source.
The cost of fish mortalities resulting from their returning
to cooler water after being attracted to heated waters in
winter may be considerable.
Rising temperatures stimulate the decomposition of sludge,
formation of sludge gas, multiplication of saprophytic
bacteria and fungi (particularly in the presence of organic
wastes), and the consumption of oxygen by putrefactive
processes, thus affecting the aesthetic value of a water
course.
In general, marine water temperatures do not change as
rapidly or range as widely as those of fresh waters. Marine
and estuarine fishes, therefore, are less tolerant of
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temperature variation. Although this limited tolerance is
greater in estuarine than in open water marine species,
temperature changes are more important to those fishes in
estuaries and bays than to those in open marine areas,
because of the nursery and replenishment functions of the
estuary that can be adversely affected by extreme
temperature changes.
Boron
Never found in nature in its elemental form, boron occurs as
sodium borate (borax) or as calcium borate (colemanite) in
mineral deposits and natural waters of Southern California
and Italy. Elemental boron is used in nuclear installations
as a shielding material (neutron absorber). It is also used
in metallurgy to harden other metals.
Boric acid and boron salts are used extensively in industry
for such purposes as weatherproofing wood, fireproofing
fabrics, manufacturing glass and porcelain and producing
leather, carpets, cosmetics and artificial gems. Boric acid
is used as a bactericide and fungicide and boron, in the
form of boron hydrides or borates, is used in high energy
fuels.
Boron is present in the ordinary human diet at about 10 to
20 mg/day, with fruits and vegetables being the largest
contributors. In food or in water, it is rapidly and
completely absorbed by the human system, but it is also
promptly excreted in urine. Boron in drinking water is not
generally regarded as a hazard to humans. It has been
reported that boron concentrations up to 30 mg/1 are not
harmful.
Cadmium (Cd)
Cadmium is a relatively rare element that is seldom found in
sufficient quantities in a pure state to warrant mining or
extraction from the earth's surface. It is found in trace
amounts of about 1 ppm throughout the earth's crust.
Cadmium is, however, a valuable by-product of zinc
production.
Cadmium is used primarily as a metal plating material and
can be found as an impurity in the secondary refining of
zinc, lead, and copper. Cadmium is also used in the
manufacture of primary cells of batteries and as a neutron
adsorber in nuclear reactors. Other uses of cadmium are in
the production of pigments, phosphors, semi-conductors,
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electrical contactors, and special purpose low temperature
alloys.
Cadmium is an extremely dangerous cumulative toxicant,
causing insidious progressive chronic poisoning in mammals,
fish, and probably other animals because the metal is not
excreted. Cadmium could form organic compounds which might
lead to mutagenic or teratogenic effects. Cadmium is known
to have marked acute and chronic effects on aquatic
organisms also.
Toxic effects of cadmium on man have been reported from
throughout the world. Cadmium is normally ingested by
humans through food and water and also by breathing air
contaminated by cadmium. Cadmium in drinking water supplies
is extremely hazardous to humans, and conventional
treatment, as practiced in the United States, does not
remove it. Cadmium is cumulative in the liver, kidney,
pancreas, and thyroid of humans and other animals. A severe
bone and kidney syndrome in Japan has been associated with
the ingestion of as little as 600 ug/day of cadmium. The
allowable cadmium concentration in drinking water is set as
low as 0.01 mg/1 in the U. S. and as high as 0.10 mg/1 in
Russia.
Cadmium acts synergistically with other metals. Copper and
zinc substantially increase its toxicity. Cadmium is
concentrated by marine organisms, particularly molluscs,
which accumulate cadmium in calcareous tissues and in the
viscera. A concentration factor of 1000 for cadmium in fish
muscle has been reported, as have concentration factors of
3000 in marine plants, and up to 29,600 in certain marine
animals. The eggs and larvae of fish are apparently more
sensitive than adult fish to poisoning by cadmium, and
crustaceans appear to be more sensitive than fish eggs and
larvae.
Chromium (Cr)
Chromium is an elemental metal usually found as a chromite
(FeCr20UJ. The metal is normally produced by reducing the
oxide with aluminum.
Chromium and its compounds are used extensively throughout
industry. It is used to harden steel and as an ingredient
in other useful alloys. Chromium is also used in the
electroplating industry as an ornamental and corrosion
resistant plating on steel and can be used in pigments and
as a pickling acid (chromic acid).
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The two most prevalent chromium forms found in industry
waste waters are hexavalent and trivalent chromium. Chromic
acid used in industry is a hexavalent chromium compound
which is partially reduced to the trivalent form during use.
Chromium can exist as either trivalent or hexavalent
compounds in raw waste streams. Hexavalent chromium treat-
ment involves reduction to the trivalent form prior to
removal of chromium from the waste stream as a hydroxide
precipitate.
Chromium, in its various valence states, is hazardous to
man. It can produce lung tumors when inhaled and induces
skin sensitizations. Large doses of chromates have
corrosive effects on the intestinal tract and can cause
inflammation of the kidneys. Levels of chromate ions that
have no effect on man appear to be so low as to prohibit
determination to date. The recommendation for public water
supplies is that such supplies contain no more than 0.05
mg/1 total chromium.
The toxicity of chromium salts to fish and other aquatic
life varies widely with the species, temperature, pH,
valence of the chromium and synergistic or antagonistic
effects, especially those of hard water. Studies have shown
that trivalent chromium is more toxic to fish of some types
than hexavalent chromium. Other studies have shown opposite
effects. Fish food organisms and other lower forms of
aquatic life are extremely sensitive to chromium and it also
inhibits the growth of algae. Therefore, both hexavalent
and trivalent chromium must be considered harmful to
particular fish or organisms,
Cyanide (CN)
Cyanide is a compound that is widely used in industry
primarily as sodium cyanide (NaCN) or hydrocyanic acid
(HCN). The major use of cyanides is in the electroplating
industry where cyanide baths are used to hold ions such as
zinc and cadmium in solution. Cyanides in various compounds
are also used in steel plants, chemical plants, photographic
processing, textile dying, and ore processing.
Of all the cyanides, hydrogen cyanide (HCN) is probably the
most acutely lethal compound. HCN dissociates in water to
hydrogen ions and cyanide ions in a pH dependent reaction.
The cyanide ion is less acutely lethal than HCN. The
relationship of pH to HCN shows that as the pH is lowered to
below 7 there is less than 1% of the cyanide molecules in
the form of the CN ion and the rest is present as HCN. When
the pH is increased to 8, 9, and 10, the percentage of cya-
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nide present as CN ion is 6.7, i»2, and 87%, respectively.
The toxicity of cyanides is also increased by increases in
temperature and reductions in oxygen tensions. A
temperature rise of 10°C produced a two- to threefold
increase in the rate of the lethal action of cyanide.
In the body, the CN ion, except for a small portion exhaled,
is rapidly changed into a relatively non-toxic complex
(thiocyanate) in the liver and eliminated in the urine.
There is no evidence that the CN ion is stored in the body.
The safe ingested limit of cyanide has been estimated at
something less than 18 mg/dayr part of which comes from
normal environment and industrial exposure. The average
fatal dose of HCN by ingestion by man is 50 to 60 mg. It
has been recommended that a limit of 0.2 mg/1 cyanide not be
exceeded in public water supply sources.
The harmful effects of the cyanides on aquatic life is
affected by the pH, temperature, dissolved oxygen content,
and the concentration of minerals in the water. The
biochemical degradation of cyanide is not affected by
temperature in the range of 10 degrees C to 35 degrees C
while the toxicity of HCN is increased at higher
temperatures.
On lower forms of life and organisms, cyanide does not seem
to be as toxic as it is toward fish. The organisms that
digest BOD were found to be inhibited at 1.0 mg/1 and at 60
mg/1 although the effect is more one of delay in exertion of
BOD than total reduction.
Certain metals such as nickel may complex with cyanide to
reduce lethality, especially at higher pH values. On the
other hand, zinc and cadmium cyanide complexes may be
exceedingly toxic.
Pollutants of Specific Significance
Review of analytical data indicate that the pollutants of
special significance in the photographic processing industry
are cyanide and silver in various forms.
Ferrocyanide
Ferrocyanide concentrations were determined through a visual
determination method developed by the American National
Standards Institute. This analysis is not a standard
method, but the results serve as a reasonable guide for
differentiating between the various forms of cyanide when
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used in conjunction with the results from the total cyanide
determination.
The ferrocyanide ion, Fe(CN)£-*r comes from the bleach used
in some color processes, i.e., ferricyanide bleach.
Ferrocyanide is one of the most objectionable pollutants
resulting from photographic processing. Primarily, the
complexed ion is potentially harmful because it is converted
to free, highly toxic cyanide in the presence of sunlight.
Ferrocyanide concentration was 4.7 mg/1 in the wastewater
discharge from plant 34.
Complex cyanides (ferro- and ferricyanide) in industrial
wastewaters impose a direct threat upon the environment.
However, methods to recover or destroy these compounds are
currently employed in the photographic processing industry.
This compound represents a potential hazard in the form of
toxic cyanide ion, and since it is not easily biodegraded in
municipal secondary treatment plants, it must be treated at
its source.
Lurfe and Panova have shown that ferrocyanide first oxidizes
to ferricyanide with air in water and then photochemically
oxidizes to iron hydroxide, hydrocyanic acid and simple
soluble cyanides. The proposed mechanism is:
4 Fe(CN)6-* + O2 + 2 H20 = 4 Fe(CN)j>~3 + 4 OH~
4 Fe(CN)j6-3 + 12 H20 = 4 Fe(OH)3 + 12 HCN + 12 CN~
Overall Reaction:
4 Fe(CN)j>-« + O2 + 14 H2O +hv 4 Fe(OH)_3 +12 HCN
+ 4 OH- +12 CN-
They report that the rate of oxidation of ferrocyanide in
the presence of sunlight leaves about 25% of the original
concentration in five days..,..the ferrocyanide disappearing
completely in 10-12 days.
A recent government report has confirmed the increased
toxicity of complex cyanides from photographic wastes in the
presence of sunlight. The results of various tests show
that the conversion of complex cyanide to volatile cyanide
(HCN) is probably reversible and product limited. The
testing was carried out using an Ektachrome photographic
waste similar to all commercial film processing ferricyanide
bleaches.
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Ferrocyanide can be oxidized to ferricyanide in overflow
photographic color process bleaches using ozone and the
waste bleach recirculated for reuse in the process. Dilute
concentrations of ferricyanide can be destroyed using ozone
or chlorine under proper conditions of temperature, pH, and
catalyst addition (for chlorination only). Since there are
obvious economic advantages for reducing the discharge of
ferrocyanides, no plant should be allowed to continue to
dump waste waters containing harmful concentrations of this
compound.
Silver (Ag)
Silver is by far the most prevalent among the heavy metals
in photographic processing wastewaters. Most of the silver
enters the wastewater stream from either the fix or bleach-
fix bath overflow. At this point, silver is usually in a
soluble complex form as silver thiosulfate, and is somewhat
less toxic than ionic silver, but it can and often exists in
other forms. As reported in one study, essentially no free
silver ion results from photographic processing operations.
Silver measured in the effluent from plant 34 was 0.26 mg/1.
Silver is a soft lustrous white metal that is insoluble in
water and alkali. It is readily ionized by electrolysis and
has a particular affinity for sulfur and halogen elements.
In nature, silver is found in the elemental state and
combined in ores such as argentite (Ag2_S) , cerargyrite
(AgCl) , proustite (Ag_3AsS^) , and pyrargyrite (Ag_3SbS^3) .
From these ores, silver ions may be leached into ground
waters and surface waters, but since many silver salts such
as the chloride, sulfide, phosphate, and arsenate are
insoluble, silver ions do not generally occur in significant
concentration in natural waters.
While silver itself is not considered to be toxic, most of
its salts are poisonous due to anions present. Silver
compounds can be absorbed in the circulatory system and
reduced silver deposited in the various tissues of the body.
A condition known as argyria, a permanent greyish
pigmentation of the skin and mucous membranes, can result.
Concentrations in the range of O.U-1 mg/1 have caused
pathological changes in the kidneys, liver and spleen of
rats.
According to Kodak researchers, silver is usually
solubilized as the tightly formed thiosulfate complex during
processing of photographic paper and film. The predominant
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complex formed in the fixing bath after development is
Ag(S203)J2-3.
A second method of removing silver from film which does not
utilize the thiosulfate fixing processes is found in certain
black-and-white reversal processes. This method involves
the use of silver solvent bleaches containing potassium
dichromate and sulfuric acid (or sulfamic acid). The silver
metal is oxidized by the dichromate and is solubilized as
silver sulfate or silver sulfamate. Silver is precipitated
from these bleaches by halides, or complexed by thiosulfate.
Silver will exist as insoluble silver bromide (AgBr), silver
sulfide (Ag^S) or soluble, silver thiosulfate complex.
A third type of process is the wash-off process, in which
non-image silver is removed by washing off the emulsion
containing either silver halides or metallic silver. Since
there is no silver complexing agent in these processes, the
concentration of dissolved silver would be limited by the
solubility of the most soluble silver halide present.
Silver bromide is commonly used in this type of emulsion and
has a solubility product of 4.8 x 10~i3 at 25 C. The 1962
U.S. Public Health Service drinking water standards limit
the concentration of silver to 0.05 mg/1 (ppm).
Eastman Kodak Company respirometric studies (Warburg)
indicate no toxicity to unacclimated activated sludge by
silver thiosulfate at silver levels of 100 mg/1. In fact,
there is a 17% stimulation of oxygen uptake due to the
presence of thiosulfate. On the other hand, 10 mg/1 of
freely dissociable silver nitrate (AgNO3J results in about
an BH% inhibition. Extremely insoluble silver sulfide has
no effect at 100 mg/1. It is evident that the toxicity of
silver to biological treatment plants is dependent upon the
free silver ion concentration.
Silver Analyses from Influent and Effluent of Eastman
Kodak Company * s King's Landing Water Purification Plant
Data from the Kodak King's Landing Water Purification Plant,
a 36 mgd (136,260 Cu m/day) activated sludge plant, indicate
that silver is removed by the plant with an efficiency in
the range of 70 to 80 percent. The influent silver to this
plant comes not only from photoprocess waste, but also from
manufacturing operations. Analyses of 7-day composites for
the entire year of 1973 showed an average influent
concentration of about 0.28 mg/1 and an average effluent
concentration of about 0.07 mg/1. These data are shown on
Table V-3. Several peak influent concentrations to the
plant ranged from 0.5 to 1.0 mg/1, but the respective
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effluent concentrations ranged from 0.04 to 0.06 mg/1. The
BOD5 reduction obtained at these peak loads ranged from 95
to 98%.
Table VI-2
Summary Data for Kodak King's Landing Plant
Influent Effluent % Ag Removal X BOD Removal
mg Ag/1 mg Ag/1
1973 Avg. 0.28 0.07 78 95.5
Extremes 0.06-1.04 <0.02-0.30 40-93 80-99
< = less than
The biological system operated at King's Landing is very
similar to those of municipal secondary facilities except
that it has a higher MLSS concentration than that of most
municipal facilities. However, it receives influent
concentrations of silver much higher than would be expected
in a municipal treatment plant and yet operates with an
efficiency of about 95?? in regard to BOD5 removal. Recent
analyses of silver concentration in the return sludge
indicate a range of 1000-3400 mg/kg dry weight (or
approximately 30-100 troy ounces per ton of dry solids).
Dye Couplers
If a coupler is to be removed from solution by use of carbon
dioxide and reclaimed for reuse, a centrifuge should be used
since it is easily cleaned and produces recovered couplers
of high purity. However, if the coupler was going to be
removed only for pollution-abatement purposes, to prevent
unwanted coupler from going into the sewer, the filter press
with filter aid would be preferred, according to a study by
Eastman Kodak in 1972.
69
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
General
The entire spectrum of wastewater control and treatment
technology is at the disposal of the photographic processing
subcategory. The selection of technology options depends on
the economics of that technology and the magnitude of the
final effluent concentration. Control and treatment
technology may be divided into two major groupings: in-
plant pollution abatement and end-of-pipe treatment.
After discussing the available performance data, conclusions
will be made relative to the reduction of various pollutants
commensurate with the following distinct technology levels:
I. Best Practicable Control Technology Currently
Available (BPT)
II. Best Available Technology Economically
Achievable (BAT)
III. Best Available Demonstrated Control Technology
(NSPS)
To assess the economic impact of these proposed effluent
limitations and guidelines, model treatment systems have
been proposed which are considered capable of attaining the
recommended RWL reduction. It should be noted and
understood that the particular systems were chosen for use
in the economic analysis only, and are not the only systems
capable of attaining the specified pollutant reductions.
There are many possible combinations of in-plant and end-of-
pipe systems capable of attaining the effluent limitations
guidelines and standards of performance suggested in this
report.
It is the intent of this study to allow the individual plant
to make the final decision about what specific combination
of pollution control measures is best suited to its
situation in complying with the limitations and standards
presented in this report.
71
-------
TABLE VII -1
NJ
WASTE DISPOSAL METHODS IN THE PHOTOGRAPHIC PROCESSING INDUSTRY
METHOD OF WASTE DISPOSAL
Direct Discharge
Municipal Sewer
Pretreatment Prior to
Municipal Sewer
On-Site Treatment
SILVER RECOVERY
Metallic Replacement
Electrolytic
Other
None
BLEACH REGENERATION
Persulfate
Ozone
Aeration
None
BLEACH-FIXER
Regeneration
No Regeneration
TOTAL (237)*
(212)*
6.12
83. 5$
8 %
9 %
(19D
66 %
36 %
5.2%
5.8%
(179)
55.8%
1.7%
4.5%
1*2.5%
(72)
85 %
15 %
1000 gal/
day (27)
(25)
4 %
88 %
0 %
8 %
(22)
50 %
9.1%
4.5%
ill %
(5)
20 %
0 %
40 %
40 %
W
50 %
50 %
1000-10000
gal/day (92)
(83)
6 %
89 %
7.2%
7.2%
(78)
75.7%
23.1%
3.4%
7-7%
(79)
49.3%
0 %
2.6%
50.7%
(35)
80 %
20 %
10000-50000
gal/day (64)
(60)
10 %
73.5%
6.7%
21.7%
(55)
65.5%
49.1%
7.3%
n "l
U /0
(54)
74.2%
0 %
5.4%
25.8%
(22)
95.5%
4.5%
50000
gal/day (28)
(28)
3.5%'
96.5%
25 %
3.5%
(27)
66.7%
74 %
3.7%
0 %
(27)
70 %
7.5%
0 %
22.5%
(9)
100 %
0 %
Unknown
gaVday(26)
(15)
0 %
80 %
0 %
20 %
(9)
22 %
22 %
11 %
45 %
(7)
14.3%
14.3%
14.3%
71.4%
(2)
50 %
50 %
*Number of Photographic Processing Plants is Indicated in Parentheses
6/30/76
-------
TABLE VII -1 (CONTINUED)
REUSE OF
OTHER SOLUTIONS
Yes
No
REUSE OF WASH WATERS
Yes
No
USE OF SQUEEGEES
Yes
No
WASH WATER CONTROLS
Yes
No
BODc^ LOADING (Ibs/day)
10
10-100
100-500
500
TOTAL (237)*
(192)
16.758
83-3$
(176)
5.7$
94.3$
(84)
63.2$
36.8$
(107)
41 %
59 %
(227)
22.5$
48.9$
21.1$
7.5$
1000 gal/
day (27)
(20)
0 $
100 $
(22)
5 $
95 $
(8)
37.5$
62.5$
(15)
40 $
60 $
(26)
88.5$
11.5$
0 $
0 $
1000-10000
gal/day (92)
(78)
5.1$
94.9$
(79)
2.5$
97.5$
(37)
65 $
35 $
(49)
27 $
63 $
(90)
16.6$
79 $
4.4$
0 $
10000-50000
gal/day (64)
(54)
18.5$
81.5$
(46)
13 $
87 $
(28)
64.3$
35-7$
(27)
44.5$
55.5$
(62)
1.6$
45.2$
43.5$
9.7$
50000
gal/day (28)
(28)
64 $
36 $
(23)
13 $
87 %
(14)
86 %
14 $
(13)
61.5$
38.5$
(27)
0 $
3-7$
59.3$
37 $
.Unknown
gal/day (26)
(12)
0 -$
100 $
(6)
0 $
100 $
(1)
0 $
100 $
(3)
0 $
100 $
(22)
54.6$
36.4$
4.5$
4.5$
*Number of Photographic Processing Plants Is Indicated in Parentheses
6/30/76
-------
Photographic Processing
In-plant. Pollution Abatement
Regeneration and Reuse
Present state-of-the-art techniques can effectively reduce
most of the photoprocessing effluent loads. The most
advantageous system, both environmentally and economically,
is the regeneration and reuse of solutions.
Eastman Kodak Company has reported that silver and sodium
ferrocyanide are removed from all fixers before they are
sewered at their Dallas and Palo Alto processing
laboratories. Both plants discharge into municipal systems.
In addition, couplers are removed from Kodachrome solutions
before they are sewered. Coupling agents precipitated from
K-12 cyan and magenta solutions as well as from K-14 cyan,
yellow and magenta solutions are reused. Both locations
regenerate 100% of the ferricyanide bleach using the
persulfate method.
At the U.S. Naval Photographic Center in Washington, B.C.,
cost reduction procedures have resulted in significant
pollution abatement. Procedures implemented include: the
reconstitution and reuse of motion picture black and white
developers, the recovery of silver from fixing baths, and
the rejuvenation and reuse of fixing bath solutions. The
reconstitution of the processing solutions consists of
diverting chemical wastewaters from the various processing
machines to two large sump tanks prior to discharge to the
sanitary sewer. The wastewaters are pumped to the chemical
mix area as needed for chemical analyses and reconstituted
for use. Silver is recovered electrolytically from the
fixing baths. The electrolytic units recover over 90% of
the spent silver. This major military photoprocessing
installation uses eighteen processing machines and has a
wastewater flow of 150,000 gpd. Wastewater sources consist
of developer solutions, bleach solutions, fix solutions and
rinse water.
A review of in-plant pollution abatement practices tabulated
from 200 plant survey data from Kodak (Table VII-1) reflects
that over 85% of the plants recover silver, over 56%
regenerate bleach, over 30% regenerate bleach-fixer, and
over 15% reuse their solutions. In addition, this
tabulation shows that 25% of the photographic processing
plants use squeegees and 20% use wash water controls. It is
apparent that these in-plant pollution abatement practices
are well demonstrated and are found in photographic
74
-------
processing plants ranging in size from less than 1,000 gpd
to over 50,000 gpd operations.
EROS has designed a "Chemical Management System" to handle
the chemicals used at their Sioux Falls, S.D. location. The
system involves reuse of fixers, bleach/fixers, and
bleaches, and a waste destruct system which detoxifies the
chemicals before they, are discharged. The system is
controlled by a,mini-digital computer with a panel display
of actual working condition.
The "Chemical Management System" is divided into eleven
separate systems which are discussed below. Four fix
regeneration systems are used to desilver the fix with
thiosulfate and recycle the regenerated fix back to the
process. One bleach/fix recovery system is used to desilver
this formulation electrolytically. The bleach/fix is then
aerated to oxidize the ferrous ion, and then regenerated
with fresh chemicals for reuse. One bleach reuse system is
used to ozonate the used bleach. The ozone converts the
ferrocyanide to ferricyanide. The regenerated bleach is
mixed with fresh chemicals and reused.
Two waste systems are used to desilver (electrolytically)
the used fix and bleach/fix which will not be reused. The
wastewater is then pumped to the "General Waste System".
The waste bleach also has a separate treatment system. It
is treated chemically by either precipitation with ferrous
sulfate or with sodium hydroxide/sodium hypochlorite
reaction. The treated wastewater is then discharged to the
waste treatment ponds.
The tenth step of the system is the "General Waste System"
which consists of a series of tanks with ozonation in each.
This system reduces the COD from an average of 25,000 mg/1
to less than 5,000 mg/1. The ozonated water is then
discharged to the treatment ponds.
The final step of the system is a "Quick Dump System" which
holds any process dumps until the "General Waste System" can
handle the extra flow.
The waste treatment system at EROS Data Center consists of a
series of five ponds, one aerated, one settling, two
polishing, and a final lake. The system receives the
ozonated wastewater and the used chemicals which undergo
easy biodegradation (stops, stabilizers, prehardeners, and
neutralizers). On a yearly average, the treatment system
has achieved a COD of 30 mg/1, ferrocyanide of 0.05 mg/1 and
a total silver of 0.006 mg/1.
75
-------
A. Silver Recovery
Basically there are four methods of recovering silver from
photographic processing solutions: metallic replacement,
electrolytic plating, ion exchange and chemical
precipitation. These methods can be used singly or in
combination, depending on which is most suitable for the
particular needs of the user. These four methods are
examined in detail.
Metallic Replacement
Metallic replacement occurs when a metal, such as iron,
comes in contact with a solution containing dissolved ions
of a less active metal, such as silver. The dissolved
silver, which is present in the form of a thiosulfate
complex, reacts with solid metal (iron) ; the more active
metal (iron) goes into solution as an ion, and an ion of the
less active metal becomes solid metal (silver).
Silver ions will displace ions of many of the common metals
from their solid state. Zinc or iron can be used to recover
silver from fixes. Because of its economy and convenience,
steel wool is the form of metal used most often.
Furthermore, the zinc that would be carried into the drain
is potentially a pollutant. Its use, therefore, is not
generally considered acceptable from an environmental
standpoint.
The acidity of the fix is an important factor when using
steel wool in the recovery of silver. Below a pH of 4, the
dissolution of the steel wool is too rapid. Above a pH of
6.5, the replacement reaction may be so slow that an
excessive amount of silver may be lost because of the long
reaction time required to recover the silver. Silver loss
in this case will depend on the flow rate through the
reaction cartridge.
Silver recovery by metallic replacement is most often
carried out using commercially available cartridges
consisting of a sealed plastic bucket containing steel wool.
The fixer that comes out of a steel wool cartridge will
usually contain less than 50 mg/1 silver. Common practice
is to replace the cartridge when the silver reaches 1,000
mg/1, as shown on a silver test paper. With careful
maintenance, 90ft or more of the silver in the fixer can be
recovered by this method.
76
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Electrolytic Recovery
In the electrolytic method of recovery, silver is removed
from fixing baths by passing a controlled, direct electrical
current between two electrodes (cathode and anode) suspended
in the fixer solution. Silver is deposited on the cathode
in the form of nearly pure silver plate. The cathodes are
removed periodically, and the silver is stripped off.
Electrolytic systems can be installed in two basic ways.
One is to de-silver the fixer overflow from a processing
machine as it flows to the sewer. The system can be
operated for either a batch or a continuous flow cell.
Another method is to remove silver from the fixer in a
continuously recirculating in-line system at approximately
the rate at which silver is being added by processing. The
latter procedure has the advantage of maintaining a low
silver concentration in the processing bath so that the
amount of silver carried out with the fixer into the wash
tanks is minimal. A modification of the circulating system
can collect fixer overflowing from several processing
machines, deliver it in a separate electrolytic system, and
then reconstitute the de-silvered fixer to supply the
processing equipment again where recommended by the
manufacturer.
In-line electrolytic silver recovery can maintain the silver
concentration in a recirculated fixer system between 500
mg/1 and 1,000 mg/1. When used as a tailing or terminal
treatment, a silver concentration of 20 mg/1 to 50 mg/1 can
be achieved.
Ion Exchange
Ion exchange is a unit process in which ions held by
electrostatic forces to charged functional groups on the
interior of a polymer bead are exchanged for ions in a
solution.
Ion exchange is a method of removing certain dissolved
solids from water. During the removal process, wastewater
is percolated through a column or bed of ion-exchange
material. Ion exchangers are very similar in construction
to pressure-type sand filters, except that an ion-exchange
material such as zeolite replaces the sand. The ion-
exchange material has the capacity to replace mineral ions
in the water with ions from inside the zeolite. No
chemicals are added during the exchange process. Eventually
the ion-exchange capacity of the zeolite is exhausted and it
77
-------
is then necessary to regenerate it by addition of a
chemical.
A number of synthetic ion-exchange resins have been
developed making it now possible to remove either or both
anions and cations from the solution. The most common set
up is to run the ion-exchange columns in series but any
combination can be set up depending on the requirements of
the specific situation.
When resins are exhausted they must be regenerated; an acid
is used to supply hydrogen ion to a cation resin, and a base
is used to supply hydroxyl ions to an anion resin. Where
water reuse is mandatory, it can be used to keep down the
buildup of certain undesirable dissolved solids. The water
that is put through the ion exchange process should first
have had as much of the dissolved organics removed as
possible in order to minimize the danger of fouling the
resin. Ion-exchange units can remove silver to virtually
nondetectable limits from a waste stream if operated
properly.
Sulfide Precipitation
Silver may be precipitated from fixers and their washes with
sodium sulfide. The precipitation is quantitative in an
alkaline solution, and the resultant silver sulfide is one
of the most insoluble substances known. It has a solubility
product of about 10~5°. The physical characteristics are
not as favorable as the chemical characteristics. Silver
sulfide tends to form colloidal suspensions. Its very small
particle size makes filtration difficult, and the filter
cake produced is extremely dense. Diatomaceous earth filter
aid can be used to improve filtration. About three grams of
filter aid are required for each gram of silver if a
conventional filter press is used.
With sulfide precipitation it is possible to remove
virtually all the silver from both the fixer and the wash
following the fixer. Tests on experimental equipment have
given results of less than 0.5 mg/1. The actual
concentration usually depends on the efficiency of the
filtering or settling step. Any silver lost is in the form
of insoluble silver sulfide particles.
B. Regeneration of Ferricyanide Bleach
The basis for all the regeneration methods is the use of a
sufficiently strong oxidizing agent that has reaction
products compatible with or used in the process. Since
78
-------
bromide is required in the bleach formula, bromate, bromite,
and elemental bromine have been used. Persulfate can be
used because some sulfate can be tolerated. Ozone, hydrogen
peroxide, and electrolytic oxidation have also been used
because they leave no chemical by-products.
Persulfate Regeneration
In actual practice, persulfate is most widely used. This
technigue has the advantages of being simple to use,
involving no significant capital expenditure, and requiring
only comparatively safe and stable chemicals. However,
regeneration of a bleach with persulfate results in a build-
up of the sulfate ion that slows the rate of bleaching. The
build-up of sulfate is higher in bleaches for reversal
products because of the comparatively large amounts of
persulfate used in the regeneration process. In some
processes, especially if squeegees are used to minimize
water carry-in, the sulfate build-up may require the
sewering of up to 10 percent of the bleach for each
regeneration cycle in order to maintain adequate bleaching.
Ozone Regeneration
This process is characterized by the following
stoichiometric reaction:
2[Fe(CN) J6J-* + H2O + O.3 = 2[Fe(CN)£]~3 + 2(OH)-» + O^
ferrocyanide water ozone ferricyanide hydroxyl oxygen
ion ion ion
The pH of the bleach increases as the reaction proceeds;
consequently, it is necessary to add acid. Bromide is
required in the bleaching process; the use of hydrobromic
acid, therefore, furnishes both the bromide and the hydrogen
ion. Theoretically, one bromide ion is required for each
ferrocyanide ion that is oxidized to ferricyanide. The
hydrobromic acid avoids all build-up of sulfate and other
unwanted products. If in practice there is a slight build-
up of bromide ion, a small amount of sulfuric acid could be
added without danger of high sulfate build-up. Likewise,
slight pH adjustments could be made with sulfuric acid.
C. Developer Recovery
Developers become exhausted both by loss of active
developing agents and by increase of reaction products. The
limiting factor is usually the increased bromide
concentration. Two approaches may be taken to reuse
developers: 1) the reaction products can be removed so
79
-------
that the bulk of the solution may be reused; or 2) specific
chemicals can be separated from the bulk of the solution and
reused with or without further purification.
Ion Exchange
Ion exchange generally can give a greater reduction in
chemical usage. As an example, bromide and developer
decomposition products can be removed by ion exchange from
Eastman Color Developers; other constituents are not
affected. After passing through an ion exchange column, the
developer is reconstituted to replenisher :strength and is
reused.
Precipitation and Extraction
The recovery of specific chemicals may not have as great an
effect on reduced chemical usage as the removal of bromide
by ion exchange, but significant cost savings can be
realized and certain non-biodegradable organics can be
removed. The most widely practiced application is the
recovery of couplers from the various color developers in
the process for Kodachrome film. The couplers are soluble
in an alkaline solution but precipitate at a neutral or acid
pH.
It is common practice to use CO2^ to adjust the solution to
pH 7 and then remove the precipitated coupler by
centrifuging. The coupler is dried, assayed, and sometimes
repurified.
Developing agents can be extracted with organic solvents
using conventional liquid-liquid-extraction techniques. One
problem is that unwanted substances are also extracted,
often making the chemical analysis of the extract difficult.
This technique is not in use at the present time and is
being considered only for possible use in the event of
shortages of certain chemicals.
D. Use of Squeegees
Effluent loads can also be minimized in the photographic
process by the correct use of mechanical aids such as
squeegees, which generally inhibit the carry-over from one
tank to the next.
There are four general locations for squeegee action in the
photographic process:
1. After the photographic solution but prior to a wash
80
-------
2. After a wash but prior to a photographic solution
3. Between two photographic solutions
H. After a wash but prior to drying
Generally, a squeegee following a photographic solution will
have relatively little effect on the replenishment rate of
that solution. An exception to this would be the first
solution in thfe sequence, such as a developer or
prehardener. The first solution is usually alkaline and
causes a considerable swelling of the gelatin; consequently,
large amounts of chemicals are included in the swollen
emulsion. Solution removed in this manner is not replaced
by carry-over from any previous solution. The squeegee
action here will retain most of the solution on the surfaces
of the film, thus possibly reducing the replenishment rate.
The advantage of the squeegee in this situation, however, is
not only to reduce the replenishment rate, but to increase
chemical recovery. The squeegee prevents the processing
solution from being transported by the film to the wash
water which is generally discarded. Instead it allows more
of the solution to overflow where it is collected and ulti-
mately reused or treated to remove unwanted materials.
The squeegee following a wash, like the processing solution
discussed, will have little effect on the wash itself.
Again, the water must go somewhere and if the squeegee
removes it from the film, the resulting build-up of water
will simply go out the overflow if the wash rates are not
reduced accordingly. The important effect of the squeegee
in this instance is evident by a reduction in replenishment
in the next bath caused by the reduction in dilution water.
The reduction of dilution water results in higher
concentration in the bath, which generally means both a cost
savings to the processor and fewer chemical pollutants going
to the sewer.
Careful study is required when considering a squeegee
between two photographic solutions. There may be some
interdependence between the two chemical baths that were
designed into the process. By placing a squeegee between
them, the equilibrium could be upset, thus reducing the
effectiveness of the process. A detailed list of advantages
and disadvantages of squeegees is shown in Table VII-2,
E. Use of Holding Tanks
Large-scale processors operate on a continuously replenished
system, not in batches. Normal operations require no
81
-------
TABLE VII -2
Squeegee Summary
Squeegee Type
Vacuum
Air
Rubber
Offset
Polyurethane
Spring Loaded
Polyurethane
Advantages
1. Power requirement less
than air squeegee
2. Moisture carried away
frcmffilm
1. No physical contact
with film
2. Good squeegee action
3. Simplicity
1. Inexpensive
2. Simplicity
1. Good squeegee
1. Constant tension
2. Low Blade pressure
3. Self-aligning
4. High efficiency at high
film speeds
5. Size not limited
Disadvantages
1. High maintenance required
2. Film damage possible
3. Requires a vacuum source
1. Supply of oil free air
2. High noise level
3. Solution moisture -
- causing possible
c ontaminat ion
4. High maintenance required
1. High blade wear
2. Film damage possible
1. Film damage possible
2. Maintenance required
3. Lower efficiency at high
film speeds
1. Film damage possible
2. Eventual blade wear
Rotary
Buffers
1. Simplicity
2. Good squeegee action
3. Low power consumption
^4. Size not linti ted
1. Separate power drive
required
2. Maintenance for nap
wear
Wringer
Sling
1. No external power 1.
supply 2.
2. Good crossover squeegee
3- Relatively simple 3-
Film damage possible
Operation limited to
high film speeds
Fair squeegee action
82
6/30/76
-------
dumping of solutions. However, because of an emergency,
periodic shutdown, contamination, or exhaustion of
solutions, occasional disposal of a processing solution may
be necessary. If this is suddenly "dumped" untreated, it
may shock load or overload wastewater treatment facilities.
This situation can be avoided by a controlled discharge of
the solution. A holding tank large enough to hold the total
volume of solution that might be reasonably expected to be
dumped at any one time is used, and the solution in the
holding tank should be treated to remove silver and cyanides
before being bled slowly to the wastewater sewer.
End-of-pipe Treatment
A. Biological Treatment
Activated Sludge
An activated sludge pilot unit is being operated on
photographic processing wastes. BOD reductions of over 80%
have been obtained with this system while the silver
influent concentration was as high as 5 mg/1. In addition,
the sludge in the aeration tank had a silver content greater
than 250 mg/1 of silver. This silver is predominantly in
the form of insoluble silver sulfide with a smaller amount
of elemental silver. The extended aeration unit has a
capacity of 20,000 gpd and was chosen for its high potential
for BOD5 reduction and its low solids production. The
processing wastes fed to the extended-aeration plant were
collected from nine processing machines. These wastes,
which varied over a period of years, included effluents from
Ektaprint R, Ektaprint C, and Ektaprint 3 chemicals and from
the E-U, C-22, CRI-I, and K-12 processes. The effluents
from the machine flows were collected and pumped to two
1,000-gallon fiberglass holding tanks. These were used to
smooth out surges and to provide a constant source of feed
for the treatment plant and insure a constant flow to the
system.
During the first year of operation BOD5 reductions were low,
because of a combination of hydraulic overloading and poor
sludge settling characteristics, which caused high suspended
solids in the effluent. As a result, the MLSS content in
the aeration tank was low. This was remedied by the
installation of sand filters to increase MLSS by recycling
the backwash wastewater into the aeration tank. After the
sand filters were put into operation, BOD reduction
immediately improved. For example, before implementation of
the sand filters, overall BODJ reductions of 85% were
obtained only 12% of the time. After the installation of
83
-------
the filters, 85% BODJ5 reductions were obtained 64% of the
time. Simultaneously, the food to microorganisms ratio
decreased because of the MLSS increase. The pH of the
influent and effluent was monitored daily. The pH of the
influent was always alkaline, varying from 7.2 to 10.3.
More than 98% of the time, the effluent pH was between 6.5
and 8.5.
Lagoons
Lagooning and ponding are popular methods for treating
industrial and municipal wastes. However, a significant
amount of acreage is required for satisfactory treatment.
The use of surface mechanical aeration equipment or of
diffused aeration has helped lagoons become an economical
alternative in biological waste treatment of industrial
wastes.
Several processing laboratories have used lagoons for
treating their photographic processing effluent. The
overall BOD5_ reductions ranged from 30% to 90% depending
upon the loading and the use of supplemental aeration.
According to the literature a photographic processing
laboratory (plant) in suburban Detroit has been treating its
wash waters in a lagoon prior to discharge to a small
receiving stream. A second example of a successful
biological system treating photographic processing effluent
is a facility in Webster, New York. This wastewater
treatment plant utilized a two-stage aerated lagoon.
Oxygen-demand reductions were in excess of 90% and the
silver content in the lagoon systems was generally in the 1
to 5 mg/1 range. Another example is the previously
mentioned system at the EROS Data Center in Sioux Falls,
South Dakota.
B. Physical/Chemical Treatment
Ozonation
Biological treatment experiments have shown that the
photographic chemicals used in the largest quantity (such as
thiosulfate, acetate, sulfite, hydroquinone, and benzyl
alcohol) respond well to biological treatment. However, a
small percentage of chemicals (such as color-developing
agents and EDTA) appear to be biodegraded only slowly or not
at all. Consequently, ozonation, a non-biological waste
treatment system, has been tested to evaluate the
treatability of such chemicals.
84
-------
The results of these experiments are summarized in Table
VII-3. Only acetate and glycine were found to be
untreatable, and ethylene glycol, methanol, ferricyanide,
and ethylene diamine were marginally treatable;. The other
chemicals are considered treatable. However, the degree of
degradation by ozonation is subject to variation and is not
fully substantiated.
Several factors may influence the rate of ozonation of
photoprocessing wastes. These include the contact time
between gas and solution, gas bubble size and flow rate,
concentration of ozone, nature and concentration of
chemical, temperature, pressure, pH, and the presence of
catalysts.
The suggested uses of ozone are: 1) as a preliminary
treatment for overflow color developer solution; 2) as a
preliminary treatment for solutions that may contain
substantial amounts of thiocyanate, formate, EDTA, or black
and white developing agents (other than hydroquinone); and
3) as a means of tertiary treatment and disinfection for an
overall mixed waste, after that waste has first been treated
biologically.
Ozone Decomposition of Ferrocyanide
The decomposition of the ferrocyanide ion has been found to
be a very complex mechanism, involving a number of competing
reactions.
2 Fe(CN)j5-* + 03 + H20 = 2 Fe(CN)<>-3 + 2 OH~ + O2
Fe(CN)£~3 = Fe+3 + 6 CN~
Destruction of free cyanide ion
CN- +
-------
Table V I I -3
Summation of Ozonation Results
Treatable Chemicals Mon-treatable Chemicals
HAS Glycine
Benzyl Alcohol Acetate ion
Color Developing Agent
Thiosulfate
Sulfate
Hydroquinone
Kodak Elon Developing Agent
Phenidone
EDTA
Ferric EDTA Marginally Treatable
Formate Ion Chemicals
Fo rma1i n
Maleic Acid Ethylene Glycol
Eastman Color Print Effluent Methanol
Ektaprint 3 Effluent Ferricyanide
Flexicolor Effluent Ethylene Diamine
Synthetic Effluent from Combined Process Ektachrome ME-4 Effluent
86
6/30/76
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understood. Apparently, the breakdown consists of a
combination of reactions, including both hydrolysis and
oxidation.
Activated Carbon Adsorption
The feasibility of treating various photographic processing
chemicals and solutions by activated carbon is summarized in
Table VII-H.
As with ozonation, more of the photographic processing
chemicals are treatable than are untreatable.
Chemical Precipitation
Precipitation can be used effectively for the removal of
ferrocyanide and ferricyanide from photoprocessing
wastewaters. These complex ions can be precipitated by
using iron salts; ferrous sulfate has proved to be an
economical and effective precipitant.
When employing precipitation for removal of ferri-
ferrocyanide, four items must be considered: equalization,
chemical feed system, clarification, and solids handling and
disposal. The purpose of equalization is to minimize the
peaks in flow and concentration so that the treatment system
can be designed to provide reliable and consistent results.
The chemical feed system adds the precipitation chemicals in
the proper quantity at the proper point. Ferrous sulfate
dosage in the range of 250-500 mg/1 with pH of about 8.5 or
greater has been reported to give good results. The
precipitated materials may be removed in a clarifier.
The advantages of the precipitation technique for ferri-
ferrocyanide over other forms of destruction or removal are:
1) precipitation occurs instantaneously, and the system thus
requires less reaction tank capacity per unit volume of
wastes; 2) precipitation removes virtually all of the ferri-
ferrocyanide; 3) hour-to-hour fluctuations in concentration
of the waste do not significantly change the operating
characteristics; and H) the process works equally well with
a variable influent since only -the ferri-ferrocyanide in the
system reacts with iron. Disposal of the ferrocyanide
sludges presents some problems,
Reverse Osmosis
The major chemicals used in photoprocessing have been tested
to find the degree to which they are stopped by a cellulose
acetate membrane under reverse osmosis conditions. Water,
87
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Table VII -4
Feasibility of Treating Photographic Processing Chemicals w-i th Activated Carbon
Treatabl-e Solutions
>
Ektaprint 3 Mixed Effluent
Ektaprint R Color Developer
Color Developers
CD-I, CD-2, CD-3, CD-k
Anti-Calcium No. 3
Elon
Phenidone
Citric Acid
Benzyl Alcohol
Hydroqui none
Na^EDTA . 2H 0
NH^FeEDTA
Non-Treatable Solutions
Citrizinic Acid
HAS
Etliylene Glycol
Potassium Oxalate
Ferricyanide
Margi nally-Treatabl e
Solut ions
Ethylene Diamine
Formic Acid
Acetic Acid
Overal1 Photographic Effluent
88
6/30/76
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hydroquinone, and alcohol passed through the membrane
easily, but halides and the complex inorganic ions found in
fixing baths and bleaches were easily stopped. Recent
studies have confirmed that fixer wash water is easily
separated into two streams, one containing the concentrated
salts and the other stream containing nearly pure water.
Thus, it is possible to return the fixer concentrate or the
bleach concentrate to the mix area for reuse in building a
new replenisher. The fixer concentrate contains virtually
all of the silver complex that was in the wash water, and it
is now practical to remove it electrolytically.
89
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SECTION VIII
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
General
Qualitative cost information for the suggested end-of-pipe
treatment models is presented in the following discussion
for the purpose of assessing the economic impact of the
proposed effluent limitations and guidelines. An economic
analysis of treatment cost impact will be available in a
separate document.
In order to evaluate the economic impact of treatment on a
uniform basis, end-of-pipe treatment models which will
provide the desired level of treatment were proposed. In-
plant control measures have not been evaluated separately.
Although there are general cost and energy requirements for
equipment items, these correlations are usually expressed in
terms of specific design parameters. Such parameters are
related to the production rate and other specific considera-
tions at a particular production site.
In this point source category, there is a wide variety of
process plant sizes and unit operations. Many detailed
designs might be required to develop a meaningful
understanding of the economic impact of process
modifications. Such a development is really not necessary,
however, because the end-of-pipe models are capable of
attaining the recommended effluent limitations. An optional
biological design for an end-of-pipe treatment model has
been provided. In addition, in-plant modification costs for
a 20,000 gpd flow system which incorporates electrolytic
silver recovery, squeegees on photoprocessing machines and
bleach regeneration are presented. Costs for these in-plant
changes for this size system is approximately $67,000 on an
installed basis. These in-plant controls constitute the BPT
treatment model. These models can be related directly to
the range of influent hydraulic and organic loading within
each plant. Costs associated with these systems can be
divided by the production rate to show the economic impact
of the system in terms of dollars per 1,000 square feet of
product or dollars per 1,000 square meters of product. The
combination of in-plant controls and end-of-pipe treatment
used to attain the effluent limitations, guidelines and new
source performance standards presented in this document
should be a decision made by the individual plant based
generally upon economic considerations.
91
-------
The major non-water quality consideration associated with
in-process control measures is the means of ultimate
disposal of wastes. As the volume of the process RWL is
reduced, alternative disposal techniques such as in-
cineration, pyrolysis, evaporation, ocean discharge, and
deep-well injection become more feasible. Becent
regulations tend to limit the use of ocean discharge and
deep-well injection because of the potential long-term de-
trimental effects associated with these disposal procedures.
Incineration and evaporation are viable alternatives for
concentrated waste streams. considerations involving air
pollution and auxiliary fuel requirements, depending on the
heating value of the waste, must be evaluated individually
for each situation.
Other non-water quality aspects such as noise levels will
not be perceptibly affected by the proposed wastewater
treatment systems. Equipment associated with in-process and
end-of-pipe control systems would not add significantly to
current noise levels.
Extensive annual and capital cost estimates have been
prepared for the end-of-pipe treatment models to evaluate
the economic impact of the proposed effluent limitations and
guidelines. The capital costs were generated on a unit
process basis (e.g., equalization, neutralization, etc.) and
are reported in the form of cost curves in Supplement A for
the proposed treatment systems. The particular cost curves
used in the treatment models for photographic processing are
shown later in this section under the paragraphs titled BPT
Cost Model and BAT Cost Model. The following percentage
figures were added on to the total unit process costs to
develop the total capital cost requirements:
Percent of Unit Process
Item Capital Cost
Electrical 14
Piping 20
Instrumentation 8
Site Work 6
Engineering Design and construction
Surveillance Fees 15
Construction Contingency 15
Land costs were computed independently and added directly to
the total capital costs.
Annual costs were computed using the following cost basis:
92
-------
Item
Capital Recovery
plus Return
Operations and
Maintenance
Energy and Power
Cost Allocation
10 yrs at 10 percent
Includes labor and supervision,
chemicals, sludge hauling and dis-
posal, insurance and taxes (computed
at 2 percent of the capital cost),
and maintenance (computed at 1 per-
cent of the capital cost).
Based on $0.02/kw hr for electrical
power and 170/gal for grade 11
furnace oil.
The 10-year period used for capital recovery is acceptable
under current Internal Revenue Service regulations
pertaining to industrial pollution control equipment.
The following is a qualitative as well as a quantitative
discussion of the possible effects that variations in
treatment technology or design criteria could have on the
total capital costs and annual costs.
Capital
Cost Differential
1. The cost reduction
could be 20 to UO per-
cent of the proposed
figures.
2. Cost reduction could
be 20 to 30 percent
of the total cost.
Technology or Design Criteria
Use aerated lagoons and
sludge dewatering lagoons
in place of the proposed
treatment system.
Use earthen basins with
a plastic liner in place
of reinforced concrete con-
struction, and floating
aerators with permanent-
access walkways.
Place all treatment tankage
above grade to minimize
excavation, especially if
a pumping station is re-
quired in any case. Use
all-steel tankage to
minimize capital cost.
Minimize flows and maximize 4. Cost differential would
3. Cost savings would
depend on the in-
dividual situation.
93
-------
concentrations through ex- depend on a number of
tensive in-plant recovery and items, e.g., age of
water conservation, so that plant, accessibility
other treatment technologies, to process piping,
e.g., incineration, may be local air pollution
economically competitive. standards, etc.
All cost data were computed in terms of August 1972 dollars,
which corresponds to an Engineering News Records index (ENR)
value of 1780.
This section provides quantitative cost information relative
to assessing the economic impact of the proposed effluent
limitations on the photographic processing point source
category. In order to evaluate the economic impact on a
uniform treatment basis, end-of-pipe treatment models are
proposed which will provide the desired level of treatment:
End-of-Pipe
Technology Level Treatment Model
BPT In-plant modifications
NSPS BPT plus cyanide destruction,
dual-media filtration and
ion exchange
BAT BPT plus cyanide destruction,
dual-media, filtration and
ion exchange
The combination of in-plant controls and end-of-pipe
treatment used to attain effluent limitations and guidelines
is left up to the individual manufacturer to choose on the
basis of cost-effectiveness.
BPT Cost Model/In-Piant Modification Costs
Cost estimates obtained from an industry source for a 20,000
gallons per day system is as follows:
Electrolytic silver recovery $22,000
Squeeges on machines 5,460
Bleach regenerators 40,000
Total Installed Cost $67,570
94
-------
Biological Cost Model
Activated sludge treatment process has been selected as an
alternate treatment system. The 20,000 gpd activated sludge
facility was not chosen as the model for BPT treatment for
economic reasons. The BPT cost model is based on in-plant
modifications only. Performance data on other end-of-pipe
treatment systems presently on line were insufficient.
Furthermore, a survey of the photographic processing
subcategory indicated that there are no full plant scale
end-of-pipe wastewater treatment systems.
The application of the activated sludge treatment scheme in
the photographic processing subcategory was made because of
the success encountered by the system in reducing BODji.
Average BOD5 removals from this process were 70%. Higher
BOD5 removals (perhaps as much as 85%) are possible by
increasing the size of the equalization tank used in the
biological model plant. This slight design change will
allow the treatment process to accomodate variable incoming
flows without adversely affecting performance. Also,
allowances were made in the proposed biological system to
handle any excessive sludge produced by the upgraded treat-
ment process. Figure VIII-1 illustrates the unit processes
included in the treatment system. A summary of the general
design basis for this system is presented in Table VIII-1.
Cost curves used to compute capital costs for biological
model are:
Figure Cost Curve Description
VIII-3 No. 1 Equalization Basin
VIII-U No. 5 Aeration Basin
VIII-5 No. 5B Fixed Mounted Aerators
VIII-6 No. 2,6 Primary & Secondary Clarifier
VIII-7 No. 7 Sludge Thickeners
Specific in-plant modifications aimed to reduce both the
silver and ferrocyanide concentrations in the wastewater
flow should be incorporated into end-of-pipe treatment.
These in-plant changes are considered part of good
housekeeping practice; modifications include electrolytic
silver recovery from the fix or bleach-fix baths,
regeneration of the ferricyanide bleach by ozone, using
ferric EDTA bleach in some processes after evaluating the
respective effectiveness, using squeegees, and collecting
the spent concentrated solutions in a holding tank for
controlled bleed-off to a dilute wastewater stream.
BAT Cost Model
95
-------
FIGURE VIII -1
Biological COST MODEL
PHOTOGRAPHIC
PROCESS
UJ
o
WASTEWATER
'
~~1 AERATORS
K-* ^^ »^-.
If
EQUALIZATION 1 AERATION TANK |_
BASIN A
rFmT— -fpfRc}— — n
1 T r^XH-^x
X **i>4 ^4t,t.d
rn 1 wr^
L^g—
SLUDGE RETURN
PUMPS
TANK
EXCESS SLUDGE ( MC
I
0 (
h1 H bV iTY"1*''""*"
1 1 J v^v
siunRF ^ss^^^gE^ k -.— t,d »
STORAGE ^
SLUDGE
TRANSFER
PUMPS
1 FINAL
CLARIFIER
TO
DISPOSAL
SITE
EFFLUENT
-------
Table VIM -1
Biological Treatment System Design Summary
Treatment System Hydraulic Loading: 20.000 qpd
Equal i zatIon
For plants with less than 2^-hour/day and 7 day/week production
(as is the case for most photoprocessors), a minimum holding time
of 1.5 days is provided, with continuous discharge from the equal-
ization basin over 2k hours. Given the design flow of 20,000 gpd,
the basin size becomes 30,000 gallons.
Aeration Basin
Aeration Basins are sized on the basis of historic treatability
data collected during the survey. The aeration tank has a volume
of 20,000 gallons. Mechanical turbine blowers will be provided
to supply the air. There are sufficient phosphates and nitrates
in the wastewaters to satisfy the nutrient requirement of the
system.
Secondary Flocculator Clarifiers
Secondary flocculator-clarifiers are designed for an overflow rate
of 300 gpd/sq ft. The required surface area of the clarifier is
then 70 square feet.
Sludge Thickener
The thickener was designed on the basis of a solids loading of
6 Ibs/sq ft/day.
Final Sludge Disposal
Excess biological sludge is disposed of to a sanitary landfill by
a contract hauler.
97 6/30/76
-------
The filtration of the effluent from the alternate biological
system, using dual-media filters, was selected as the BAT
treatment system. In order to protect the ion exchange beds
for BAT removal of silver, dual-media filtration also
applies. Filtration of the effluent from the biological
treatment process would provide incremental BODj> reduction
of 33 percent. Silver measured in the effluent from the
model plant was 1 mg/1, which represents an 80 percent
reduction from the influent to the biological system.
Figures VIII-2a, VIII-2b and VIII-2c illustrate the unit
processes involved in the treatment system. A summary of
the general design basis for the system is presented in
Table VIII-2. Unit process cost curve(s) employed to
determine incremental capital costs for BAT cost filtration
model is Figure VIII-8 cost curve No. 10, Multi-Media
Filters Including Feed Well, Pumps and Sump.
Table VIII-2
BAT Treatment System Design Summary
Photographic Processing Industry
Cyanide Destruction
The ferricyanide complex may be chemically destroyed by
chlorination under alkaline conditions at pH 10 or higher.
This alkaline chlorination will completely oxidize cyanide
to carbon dioxide and nitrogen. Additional chlorine and
contact time are required to oxidize the ferricyanide
complex. A neutralization step was included after the
contact tank to bring the pH back to a normal range. The
cyanide destruct system was sized for the 5,000 ft2 and the
50,000 ft2 production plant sizes. The costs for the
systems were developed from similar systems for the
electroplating industry.
Dual-Media Filter
The filters are sized on the basis of an average hydraulic
loading of 3 gpm/sq ft. Backwash facilities are sized to
provide rates up to 20 gpm/sq ft and for a total backwash
cycle of up to 10 min. in duration. The filter media are
18" of anthracite (O.USm), 6" of sand (0.15m), and a
drainage bed of 12" (0.3m) of graded gravel.
Ion Exchange
Ion exchange is a unit process in which ions held by
electrostatic forces to charged functional groups on the
interior of a polymer bead are exchanged for ions in a
98
-------
Figure VIII-l(a)
BET Wastewater Treatment
Cost Model Flow Sheet
Raw Film
or Paper
Processing
Solutions
Wash Water
Processing Steps
Bromide
Recycled
Developer
Bath and
^
Overflow
Bleach
Recycle
Silver
Recovery
Recovered Silver
for TReprocess
5-
Paper and
Processing Film
Fix and
Wash tank
overflow.
Bleach
Regeneration
Silver waste
Discharge
Bleach Waste
Discharge
Other
Process
Steps
Waste
Total Processing
Waste discharge.
* In-Plant cost model, including squeegees.
99
6/30/76
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FIGURE VJJI-2A BAT/>^SPS WASTEWATER TREATMENT COST MQDEt
CYAWJDE DESTRUCT FLOW SHEET
100
6/30/76
-------
1
VIH-2B BAT^SPS WASTEWATER TREATMENT COST MODEL
FILTRATION FLOWSHEET
6/30/76
101
-------
I
Alfc*Ji
ftegtnertoU
I
V
1
Recovery
or Divpourt
«
Vr»-2C BAT/M5PSWASTEWAfER TREATMENT COST MODEL
ION EXCHANGE FLOWSHEET
102
6/30/76
-------
solution. Both cationic and anionic resin columns were
designed because the silver may exist in the wastewater with
either a positive or negative charge. The ion exchange
columns follow the filtration step to prevent the resins
from becoming fouled due to particulate matter. The system
design includes two columns for each type of resin in order
to have flexibility of operation. The system cost was
derived by adjusting the cost from a similar system on the
basis of flow differences. The capital costs were also
adjusted from the article to the 1780 ENR Index used
throughout this document.
NSPS Cost Model
For new plant sources, the in-plant modifications available
for reducing the raw waste loads should be applied wherever
possible. In addition, a minimum of end-of-pipe treatment
as described in the BAT treatment system subsection should
be applied; this consists of the BPT in-plant control system
plus cyanide destruction, dual-media filtration and ion
exchange for residual silver removal.
Cost
Capital and annual cost estimates were prepared for the
treatment models described above. Average process water
consumption (4,000 gal/1,000 sq ft) for the industry was
based on the average of the three plants visited and 36
plants from the NAFM field survey. Costs were developed for
an average flow rate of 20,000 gpd, as explained earlier in
Section VII under "Size of Facility." In addition, a model
was prepared for an average flow rate of 200,000 gpd. This
additional model represents the costs for a plant with an
average production of 4,650 square meters per day as
compared to the 465 square meters per day production in the
original model. The costs presented for BAT and NSPS in
these tables are incremental costs over the cost for BPT.
For example, in Table VIII-3 the total capital cost for the
average size photoprocessing plant to attain BPT effluent
limitation is $67,000. The incremental capital costs for
achieving the recommended NSPS in Table VIII-3 would be
$127,400. This cost would be in addition to the capital
investment made to achieve the BPT effluent limitation.
Tables VIII-3 and VIII-4 also illustrate RWL and effluent
limitations based on the production for an alternate
biological model plant. Percent removals for BODjj and COD
are based on past operating experience of the large-scale
activated sludge treatment process.
103
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TABLE VIII -3
Wastewater Treatment Costs for
EPT, NSPS and BAT Effluent Limitations
(EMR 1780 - August, 1972 Costs)
Photographic Processing Industry
(5,000 sq ft/day Production Rate)
Average Production 465 sq m/day
(5000 sq ft/day)
Production Days 276
Wastewater Flow - kL/day
(gpd)
kL/1,000 sq m
(gal/1,000 sq ft)
BOD Effluent Limitation3- kg BOD/1,000 sq m product 35.7'
(lbs/1000 sq. ft.)
COD Effluent Limitation3- kg COD/1,000 sq m product 123
(lbs/1000 sq. ft.)
TOTAL CAPITAL COSTS
ANNUAL COSTS
Capital Recovery plus return at 10%
at 10 years
Operating + Maintenance
Energy + Power
Total Annual Cost
Cost1 /I,000 sq m Product
Technology Level
RWL Biological Plus
In-Plant
75.7
(20,000)
163
(40dO )
.7 55
(7.50) (I-")
3 61.6
(25.1) (l2.6^
$ 247,000
$ 40,300
3^,300
700
$ 75-300
$ 587
NSPS 2
3.7
(.76 )
49 .4
(10JL )
$127,400
$ 20,770
$ 5,600
$ 600
$ 26,970
$ 210
BAT 2
3.7
(0.76)
49 .4
(10.1)
$127,400
$ 20,770
$ 5,600
$ 600
$ 26,970
$ 210
EPT4
-
-
$67,570
$11,000
$ 5,660
$ 940
$17,600
$ 137
Cost based on total annual cost
2Incremental cost over BPCTCA cost
3Long term average
4Based on in-plant alone
6/30/76
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TABLE VIII
Vfc.stewater Treatment Cc^; for
BPT, NSPSand BAT Effluert .imitations
(ENR 1780 - August, 1972 Costs)
Photographic Processing Irr.u ;try
(50,000 sq ft/day Production tete)
Technology Level
RWL
o
Ul
Average Production 4650 sq m/day
(50,000 sq ft/day)
Production Days
276
Wastewater Flow - kL/day
(gpd)
kL/1,000 sq m
(gal/1,000 sq ft)
757
(200,00))
163
(4003)
o (lbs/1000 sq.ft.)
EOD5 Effluent Limitat'.on - kg BODc/1,000 sq m Product 3G.7 (7. JO)
o (lbs/1000 sq.ft.)
COD Effluent Limitation - kg COD/1,000 sq m Product 123 (25.1)
TOTAL CAPITAL COSTS
ANNUAL COSTS
Capital Recovery plus return at 10$
Operating + Maintenance
Energy + F^wer
Total Annual Cost
Cos.1 /I,000 sq m Product
Biological Plus
In-Plant
NSPS
BAT
BPT*
5.5 (1.13)
61.6 (12.6)
$ 783,000
$ 128,000
$ 117,000
$ 6,000
$ 251,000
196
3.7 (0.76)
49.4 (10.1)
$364,200
$ 59,400
$ 33,500
$ 3,900
$ 96,800
$ 75.40
3.7 (0.76)
49.4 (10.1)
$364,200
$ 59,400
$ 33,500
$ 3,900
$ 96,800
$ 75.40r.
$120,000
$ 19,500
$ 9,900
$ 1,700
$ 31,100
$ 24.23
Cost Based on total annual cost
2Incremental cost over BPCTCA erst
3long term average
on in-plant alone.
6/30/76
-------
Tables VIII-5 and VIII-6 present a breakdown of the BPT
capital costs for the wastewater treatment systems which
apply to in-plant modifications for both production rates.
Tables VIII-7 and VIII-8 show the BAT/NSPS capital costs for
the wastewater treatment modules which include cyanide
destruction, dual-media filtration and ion exchange.
These cost estimates were prepared based on the recommended
design basis. Variations in the design basis or selection
of alternative treatment processes can have appreciable
effects on the reported capital costs, as discussed in the
General section.
Energy
The size ranges of the BPT and BAT treatment models preclude
the application of high-energy-using units such as sludge
incinerators. Therefore, the overall impact on energy
should be minimal. Table VIII-3 presents the cost for
energy and power for the treatment models for BPT, BAT, and
NSPS. The details for energy and power requirements are
included in the Supplement A.
Non-water Quality Aspects
The major non-water quality aspects of the proposed effluent
limitations encompass sludge disposal for the alternate
biological model and noise and air pollution.
The biological treatment model proposes landfilling of
biological sludge. If practiced correctly, this disposal
method will not create health hazards or nuisance
conditions. However, there is a widespread diversity of
opinion over the effects of silver leaching into ground
water supplies. Carefully controlled sludge application
should minimize these problems.
Solid waste control must be considered. Pollution
control technologies generate many different amounts and
types of solid wastes and liquid concentrates through the
removal of pollutants. These substances vary greatly in
their chemical and physical composition and may be either
hazardous or non-hazardous. A variety of techniques may be
employed to dispose of these substances depending on the
degree of hazard.
If thermal processing (incineration) is the choice for
disposal of sludge to concentrate silver in the resulting
ash for recovery purposes, provisions must be made to ensure
106
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TABLE VIII -5
SUMMARY OP CAPITAL COSTS
FOR WASTEWATER TREATMENT
Biological Plus
In-Plant Model
Unit Processes
Cat egory Photographic
Model Size 5tooo sq ft/day
Capital Cost (ENR 1780 August 197? Costs)
Low Lift Pump Station
EaualJ nation Pjasin (concrete)
EauaJization Basin Mixers
Neutralization Tanks
Lime Additions Facilities
Sulphuric Acid Additions Facilities
Itepid I'iix Tariks
Primary Flocculator Clarifier
Sludge Pumps
Aeration Basins (concrete)
Aeration Basin Aerators
Secondary Flocculator Clarr'.firr
r.ccy^lc Pumps
Nutrient Additions Facilities
Polymer Additions Facilities
Sludge Thickeners
Aerobic Digesters
Digester Aerators
Sluge Pumps
Vacuum Filters
Flow Measurement & Sampling
Subtotal A
Piping 20% of (A)
Electrical 14% of (A)
Instrumentation 8% of (A)
Sitework 6% of (A)
Land
Subtotal B
Total A & B
Engineering 15% of (A) & (B)
Contingency 15% of (A) & (B)
Subtotal C
In-Plant Modifications
GRAND TOTAL (A + B + C + In-Plant)
$21,000
$22,800
$11,200
$16,350
$22,300
$18,690
$13,083
$ 7,476
$ 5,607
$20,746
$20,746
$67,570
$ 93,^50
$ 44,856
$138,306
$ 41,492
107
$247,36B~
(rounded) $247,000
6/30/76
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TABLE VIII-5(a)
Sunmary of Capital Cost
For Wastewater Treatment
In-Plant (EPT) Model
Category; Photographies
Model Size; 5,000 sq ft/day
Unit Processes Capital Cost (ENR 1780 August, 1972 costs)
Electrolytic Silver Recovery1 $22,000
Squeegees on Machines1 $ 5,370
Bleach Regeneration $40,000
Total Capital Cost $67,570
Installation Cost Excluded
108
6/30/76
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TABLE VTII-6
SUMMARY OF CAPITAL COSTS
FOR WASTEWATER TREATMENT
Biological Plus
In-Plant Model
category
Unit Processes
Photographic
Model Size 50,OOP ft2/d
Capital Cost (ENR 1?80 August 1972 Costs)
Low Id ft Pump Station
» • ••• i concrete
Equalization Basin (Earthen W/liner )
Equalization Basin Mixers
Neutralization Tanks
Lime Additions Facilities
Sulphuric Acid Additions Facilities
Rapid Mix Tanks
Primary Flocculator Clarifier
Sludpe Pumps
Aeration Basins (concrete)
Aeration Basin Aerators
Secondary Flocculator Clar^fier
Recycle Pumps
Nutrient Additions Facilities
Polymer Additions Facilities
Sludge Thickeners
Aerobic Digesters
Digester Aerators
Sludge Pumps
Vacuum Filters
Flow Measurement & Sampling
Subtotal A
Piping 20% of (A)
Electrical 14$ of (A)
Instrumentation 8$ of (A)
Sitework b% of (A)
Land
Subtotal B
Total A & B
Engineering 15% of (A) & (B)
Contingency 15% of (A) & (B)
Subcategory C
35.000
16,000
125,000
20,000
95,000
10,000
22,000
15,000
67 , 600
47 300
27^000
20'300
10,000
,.
76,500
76,500
338,000
172,200
510,200
153,000
In-plant modification
Grand Total (A + B + C + In-Plant)
109
120,000
783,000
6/30/76
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TABLE VIII-6 (a)
Sunmary of Capital Costs
For Wastewater Treatment
In-Plant (BPT) Model
Category: Photographies
Model Size:50,OOP sq ft/day
Unit Processes Capital Cost (ENR 1780 August, 1972 costs)
Electrolytic Silver Recovery $40,000
Squeegees on Machines $ 6,000
Bleach Regeneration $46,000
Installation $28,000
Total Capital Cost $120,000
110
6/30/76
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Unit Processes
TABLE VIII-7
SUMMARY OP CAPITAL COSTS
FOR WASTEWATER TREATMENT
BAT and NSPS Model
5,000 sq. ft./ day
Category Photographic Processing
SubcatgKory 5,000 sq. ft./day
Capital Cost (ENR 1780 August 1972 Costs)
Cyanide Destruction
Multi Media Filter
Ion Exchange
Neutralization Tanks
Lime Additions Facilities
Sulphuric Acid Additions Facilities
Rapid Mix Tanks
Primary Flocculator Clarifier
Sludge Pumps
Aeration Basins
Aeration Batin Aerators
Secondary Plocculator Clarifier
Recycle Pumps
Nutrient Additions Facilities
Polymer Additions Facilities
Sludge Thickeners
Aerobic Digesters
Digester Aerators
Sludge Pumps
Vacuum Filters
Flow Measurement & r>.mpling
Subtotal A
Pi-ping
20% of (A)
Electrical
of (A)
Instrumentation
Sitework
of (A )_
"
•Land
Subtotal D
Total A & B
32,400
22,800
11,000
13,240
9,270
S,lbU
3,570
31,800
98,000
Grand Total (BAT)
$127,400
111
66,200
Engineering
Contingency
Subtotal C
1555 of (A) & (B)
15% of TA) & (B)
14,700
14,700
29,400 "
6/30/76
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TABLE VIII-8
SUMMARY OP CAPITAL COSTS
FOR WASTEWATER TREATMENT
BAT and NSPS MODEL
50,000 sq. ft./day
Unit Processes
Category Photographic Processing
Subcategory 50,000 sq.ft./day
Capital Cost (EM 1780 August 1972 Costs) •
Cyanide Destruction
37,300
Multi Media Filter
88,000
Ion Exchange
64,000
Neutralization Tanks
Lime Additions Facilities
Sulphuric Acid Additions Facilities
Rapid Mix Tanks
Primary Flocculator Clarifier
Sludge Pumps
Aeration Basins
Aeration Basin Aerators
Secondary Flocculator Clarifier
Recycle Pumps
Nutrient Additions Facilities
Polymer Additions Facilities
Sludge Thickeners
Aerobic Digesters
Digester Aerators
Sludge Pumps_
Vacuum Filters
Plow Measurement & Sampling
Subtotal A
Subtotal B
Total A & B
Engineering
of (A) & (B)
~~
42,000
Subtotar
Contingenc
42.000
Grand Total ( BAT/NSPS)
112
189,300
tiping
Electrical
Instrumentation
Sitewoi*k
20% of (A)
14% of (A)
87, of (A)
' 6% of (A)
37,860
26,500
15,140
Il,3bU
•Land -
90,860
280.200
84,000
$364,200
6/30/76
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FIGURE VIII-3
EQUALIZATION BASIN
1,000,000
o
o
g 100,000
U>
GO
10,000
CONCRETE-*
EARTHEN
W/CONC. LINER
EQUALIZATION BASIN
i ENR 1780
I I I
AUGUST, 1972
10,000
100,000
1,000,000
BASIN VOLUME, GAL.
10,000,000
6/30/76
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FIGURE VIII-4
AERATION BASIN
1,000,000
o
o
<
GO
100,000
10,000
CONCRETE
AERATION BASIN -
CONCRETE BASINS
! i
ENR: 1780 |
- AUGUST. 1972 —
10,000
100,000
1,000,000
10,000,000
BASIN VOLUME, GAL.
6/30/76
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FIGURE VIII-5
FIXED-MOUNTED AERATORS
100,000
D
cc
LU
O.
o
D
10,000
1,000
SINGLE-SPEED
TWO-SPEED
FIXED-MOUNTED AERATORS
I i
ENR 1780
AUGUST, 1972
10
100
1,000
AERATOR HORSEPOWER PER UNIT
6/30/76
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FIGURE VIII-6
PRIMARY & SECONDARY CLARIFIER
1,000,000
V)
o
o
100,000
<
CO
10,000
RECTANGULAR
CIRCULAR
PRIMARY & SECONDARY CLARIFIER
INCLUDING MECHANISM
ENR: 1780
AUGUST, 1972
100
1,000
10,000
100,000
SURFACE AREA, F+2
6/30/76
-------
FIGURE VIII-7
SLUDGE THICKENERS INCLUDING MECHANISM
1,000,000
V)
o
o
2 100,000
V)
10,000
*
1
1
10 II
(
X
X
i in
o —
' ,r»
_^
( *5TC C 1
/
r
i
i
\ —
slfc
• —
CON
>
/
o
— ',n -
— ICM" _
CRE
y
/
;TE
/
^
1
J
,'
J«
,
g.
i
3
1
— j SURFACE AREA,
SLUDGE Th
INCLUDING
1 tIMK
AUGUS
2
rT
ICKE
MECh
178C
.T, 19-
MERS
ANISM
)
72
10
100
1,000
DIAMETER, FT.
6/30/76
-------
FIGURE VIII-8
MULTI-MEDIA FILTERS INCLUDING FEEDWELL, PUMPS AND SUMP
1,000,000
OD
C/}
o
o
2 100,000
JS
VI
10,00o
MULTI-MEDIA FILTERS
INCLUDING FEEDWELL..
PUMPS, & SUMP
EIMR: 1780
AUGUST, 1972
10,000
100,000
1,000,000
10,000,000
FLOW RATE,GPD
6/30/76
-------
against entry of hazardous pollutants into the atmosphere.
Consideration should also be given to recovery of materials
of value in the wastes.
For those waste materials considered to be non-hazardous
where land disposal is the choice for disposal, practices
similar to proper sanitary landfill technology may be
followed. The principles set forth in the EPA's Land
Disposal of Solid Wastes Guidelines 40 CFR Part 211 may be
used as guidance for acceptable land disposal techniques.
Best practicable control technology as known today requires
disposal of the pollutants removed from waste waters in this
industry in the form of solid wastes and liquid
concentrates. In most cases these are nonhazardous
substances requiring only minimal custodial care. However,
some constituents may be hazardous and may require special
consideration. In order to ensure long-term protection of
the environment from these hazardous or harmful
constituents, special consideration of disposal sites must
be made. All landfill sites where such hazardous wastes are
disposed should be selected so as to prevent horizontal and
vertical migration of these contaminants to ground or
surface waters. In cases where geologic conditions may not
reasonably ensure this, adequate legal and mechanical
precautions (e.g., impervious liners) should be taken to
ensure long-term protection to the environment from
hazardous materials. Where appropriate, the location of
solid hazardous materials disposal sites should be
permanently recorded in the appropriate office of legal
jurisdiction.
Noise levels will not be appreciably affected with the
implementation of the proposed treatment models. Air
pollution should only be a consideration if sludge
incineration is selected as the waste disposal alternative.
119
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE (BPT)
General
The effluent limitations that must be achieved by all plants
by 1 July, 1977 through the application of the Best
Practicable Control Technology Currently Available (BPT) are
based upon an average of the best performance achievements
of existing exemplary plants. In those industrial
categories where an exemplary treatment plant does not
exist, the effluent limitations have been based upon levels
of technology which are currently practiced in other
industries with similar wastewater characteristics and which
can be practicably implemented by 1 July, 1977.
The development of the BPT has been based on both in-plant
and alternate end-of-pipe technology. The effluent
limitations and guidelines commensurate with the BPT have
been established on the basis of information in Sections III
through VIII of this report, and are presented in the
following sections. It has been shown that these
limitations can be attained through the application of BPT
pollution control technology.
Photographic Processing
Effluent limitations and guidelines for the photographic
processing subcategory of the photographic point source
category were developed by applying the in-plant treatment
model presented in Sections VII and VIII. The in-plant
measures include silver recovery, bleach regeneration, and
squeegee installation. These in-plant pollution abatement
techniques, except for squeegees, are in common use within
the photographic processing subcategory. Squeegees, on the
other hand, require special operational attention and
careful maintenance. The variability in this system is
discussed in Section XIII.
The design data from the activated sludge unit was the basis
of the BODJ5, COD, and silver reduction presented in Table
IX-1 under biological model. Although the effluent
limitations and guidelines for BPT may be attained by a
number of combinations of in-process and end-of-process
means, the numerical values for these guidelines were
calculated by the application of waste reduction factors
from the electroplating point source category and applied to
121
-------
Table IX -1
BPT Effluent Limitations Guidelines
Photographic Processing Industry
BPT Effluent Limitations
BPT Average of Dai]y Values
Long-Term for 30 Consecutive Days Maximum for
Subcategory Flow Raw Waste Load (RW) Average Daiiy Effluent Shal 1 Not Exceed Any One Day
L/1,000 sq m Parameter kg/1,000 sq m m./L kg/1,000 ; kg/1 ,000 kg/1,000
(gal/1,000 sq ft) (lb/1,000 sq ft) (lb/1,000 sq ft) (lb/1,000 sq ft) -(lb/1,000 sq ft)
I—i
f° Entire Industry 163,000 Ag (Silver) 0.07 ' 0.45 0.07 0.07 0.14
M (4,000) (0.015) (0.015) (0.015) (0.03)
CN (Total) 0.09 0.57 0.09 0.09 0.18
(0.019) (0.019) (0.019) (0.038)
6/30/76
-------
the BPT in-plant -treatment model for cyanide and silver
parameters.
123
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SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
General
The effluent limitations and guidelines to be achieved by
all plants by July 1r 1983 through the application of the
Best Available Technology Economically Achievable (BAT) are
based upon the very best control and treatment technology
employed by the existing exemplary plants in each industrial
subcategory. Where this level of control and treatment
technology was found inadequate for the purpose of defining
BAT, control and treatment technologies were transferred
from other point source categories or technology
demonstrated in pilot plant studies were employed for the
photographic processing subcategory.
Photographic Processing
Treatment commensurate with BAT for the photographic
processing subcategory requires the application of cyanide
destruction by alkaline chlorination, dual-media filtration
and ion exchange (to remove the silver) added to the BPT in-
plant treatment. The performance of these systems has been
discussed in Section VII.
Effluent limitations and guidelines for BAT were calculated
by applying the above reduction factors to the BPT effluent
limitations and guidelines as shown in Table IX-1.
Performance factors from Table XIII-1 were applied for
maximum day limitations and maximum thirty day limitations.
The BAT effluent limitations for silver (Ag) and for cyanide
(CN) were determined by using achievable concentration
limits from the electroplating industry for the same
treatment technology. Concentratons were converted to a
mass basis using a RWL flow of 4000 gallons per 1000 square
feet of film and/or paper processed. Concentrations used in
this technology transfer as as follows:
Maximum Day Maximum 30 day
Parameter Concentration Conce ntration
Ag 0.02 mg/1 0.01 mg/1
CN 0.10 mg/1 0.05 mg/1
The effluent limitations and guidelines for BAT are
presented in Table X-1.
125
-------
Table X -1
BAT Effluent Limitat'ons Guidelines
Photographic Processing Industry
Subcategory
Flow
L/1,000 sq m
(gal/1,000 sq ft)
BAT and BADCT Effluent Limitations
BPCTCA
Long-Term Average
Parameter Daily Effluent
kg/1,000 sq m
(lbs/1,000 sq ft)
Long-Term Average Daily
kg/1,000 sq m
(lbs/1,OOP sq ft)
Average or Da iIy Values
for 30 Consecutive Days
sha11 not exceed
kg/1 ,001) sq n
(lbs/1,000 sq ft)
Maximum Value
for Any 0".3 Day
kg/1,000 sq m
(lbs/1,000 sq ft) _
Entire Industry
163,000
(4,000)
Ag (Silver)
0.07
(0.015)
0.07
(0.015)
0.0016
(0.00034)
0.0032
(0.00067)
CN (Total)
0.09
(0.019)
0.09
(0.019)
0.008
(0.0017)
0.016
(0.0034)
6/30/76
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SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
General
The term "new source" is defined in the "Federal Water
Pollution Control Act Amendments of 1972" to mean "any
source, the construction of which is commenced after the
publication of proposed regulations prescribing a standard
of performance". Technology applicable to new sources shall
be the Best Available Demonstrated Control Technology
(NSPS)t defined by a determination of what higher levels of
pollution control can be attained through the use of
improved production process and/or wastewater treatment
techniques. Thus, in addition to considering the best in-
plant and end-of-pipe control technology, NSPS technology
are to be based upon an analysis of how the level of
effluent may be reduced by changing the production process
itself.
Photographic Processing
Best Available Demonstrated Control Technology (NSPS) for
the photographic processing point source category is based
upon the utilization of both in-process controls and end-of-
pipe process treatment technologies as proposed for BAT.
Performance standards for silver and cyanide parameters are
identical with the BAT effluent limitations, guidelines and
new source performance standards. Table XI-1 presents NSPS
performance standards for the photographic processing
subcategory of the photographic point source category.
127
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VAE j: xi-i
New Source Performance Standards
Photographic ?r x:cssing Inc.ustry
Subcategory
Flow
L L/l,000 sq m
(gal/1,000 sq ft)
BPT
Long-Term Average
Parameter Daily Effluent
"'kg/1 ,000 sq m
(lbs/1,000 sq ft)
BAT and NSFS Effluent Limitations
Long-Term Average Daily
kg/1,000 sq m
(lbs/1,000 sq ft)
Average of Daily values
for 30 Consecutive Days
sha 1 1 not exceed
kg/1 ,OOU sq m
(lbs/1,000 sq ft)
• Maximum Value
for Any One Day
kg/1,000 sq m
(lbs/1 ,000 sq ft)
{3 Entire Industry 163,000
oo (4,000)
Ag (Silver)
0.07
(0.015)
0.07
(0.015)
0.0016
(0.00034)
0.0032
(0.00067)
CN (Total)
O.C9
(0-019)
0.09
(0.019)
0.008
(0.0017)
0.016
(0.0034)
6/30/76
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SECTION XII
PRETREATMENT GUIDELINES
General
Pollutants from specific processes within this subcategory
may interfere with, pass through, or otherwise be
incompatible with publicly owned treatment works (POTWs).
The following sections examine the general wastewater
characteristics of the various industries and the
pretreatment unit operations which may be applicable to the
photographic processing industry.
Approximately 5 percent of all major photoprocessing plants
are classified as existing point sources and, therefore, are
subject to the effluent limitations contained herein. The
remaining 95 percent of the plants discharge their
wastewater to municipal treatment systems and are regulated
by the pretreatment guidelines for those systems. These
guidelines are designed to prevent plants from discharging
industrial wastewaters which would upset the treatment
processes used by the municipal system and industrial
wastewaters which would pass through the works without
adequate treatment.
The incompatible pollutants in the photographic processing
wastewater are silver and ferrocyanide. The developing
solutions, couplers and fixers may become a problem if
dumped in a slug to a treatment plant. Although most
processing plants operate on a continuous basis, dumping of
solutions occur during emergencies, periodic shutdowns,
contamination, or exhaustion of solutions. To prevent a
shock to the wastewater treatment plant, a holding tank
should be installed to permit equalization of the flow to
the treatment plant.
The most practical pretreatment of incompatible pollutants
involves regeneration and reuse of processing solutions.
Various in-process modifications are currently in use by a
majority of the Photographic Processing Industry as
indicated by the Eastman-Kodak survey (Table VII-1). In
addition to being economical for the plant, the reuse
procedures substantially reduce the pollutant loading in the
wastewater. Both silver and ferrocyanide may be recovered
and reused.
129
-------
The following in-plant controls have been discussed in
Sections VII and VIII and are recommended as pretreatment
control procedures:
1. Silver may be recovered from the solutions by any
of four methods: metallic replacement, electrolytic
plating, ion exchange, chemical precipitation.
2. The regeneration of ferrocyanide bleach may be done
by oxidation with persulfate or ozone. The Kodak
plants in Dallas and Palo Alto are regenerating
100* of the bleach.
3. Developing solutions may be cleaned for reuse by
ion exchange or precipitation and extraction.
<*. The use of squeegees is a mechanical means of
reducing the quantity of wastewater by preventing
solution carry-over between process steps and
decreasing dilution water usage.
In addition to in-plant control measures, pretreatment for
new sources would include cyanide destruction, dual-media
filtration and ion exchange.
The pretreatment standards for new sources within the
photographic processing subcategory of the photographic
point source category are as follows:
Pollutant or Pretreatment
Pollutant Property Standards
Maximum for Average of daily
any one day values for thirty
consecutive days
shall not exceed
(Metric units) kg/1000 m2 of product
Ag (Silver) 0.0032 0.0016
CN(Total Cyanide) 0.016 0.008
pH Within the range 6.0 to 9.0.
(English units) lb/1000 sq ft of product
Ag(Silver) 0.00067 0.0003U
CN (Total Cyanide) 0.0034 0.0017
pH Within the range 6.0 to 9.0.
130
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Table XI I -1
Pretreatment Unit Operations
Bioloyical System
Bio log!col System
I independent Physical
Chemical System
Physical methods and
chemical precipitation
+ solids separation +
equa1izat ion
Physical methods and
chemical precipitation
+ solids separation +
equa1i zat i on
Physical methods and
chemical precipitation
+ solids separation +
equa1izat ion
131
6/30/76
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Cost to implement these abatement measures are estimated to
be equivalent to the incremental costs shown in Tables VIII-
3 and VIII-4 for 5000 square foot per day and 50,000 square
foot per day NSPS treatment models respectively. The 150
square meter per day and below facilities would be given an
exemption based on economic impact except for cyanide
destruction, equalization of flow and neutralization as is
done in the electroplating industry.
New York is the only state specifically limiting the
discharge of complex cyanides into receiving waters. The
limit is O.U mg/1 Fe(CN)6.
Due to the conversion of complex cyanides to toxic simple
cyanides, the complex should be converted to the equivalent
amount of cyanide (CN) and treated prior to discharge to a
receiving stream. The range of sewer codes for cyanide is
0.0 to 10.0 mg/1 while the range in stream standards is 0.0
to 1.0 mg/1. These values depend upon the specific city,
stream, point of entry, etc., but represent a reasonable
range of concentrations that cyanide treatment equipment
should be capable of meeting.
The yearly discharge of cyanide salts from photographic
sources has been estimated at over 5,000,000 pounds.
132
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SECTION XIII
PERFORMANCE FACTORS FOR TREATMENT
PLANT OPERATIONS
General
Variations in the performance of wastewater treatment plants
are usually attributable to one or more of the following:
1. Severe ambient air temperature changes. Although
ambient temperature changes may not be controlled,
design features such as injection of steam or hot
water can be incorporated that will minimize these
effects.
2. Variations in sampling techniques and analytical
methods do not affect the performance of a waste
treatment system but may result in false or
incorrect evaluation of such systems performance.
Establishment and use of standard methods can
eliminate apparent variations.
3. Variations in one or more operational parameters,
e.g., the organic removal rate by the biological
mass, settling rate changes of biological sludge.
These are usually the result of changing flow or
waste loadings and the addition of an equalization
tank normally takes care of this problem.
5. Controllable changes in the treatability
characteristics of the process wastewaters even
after adequate equalization. Good tight operating
practices and training skilled operators and
personnel will aid in reducing this type of
variation in treatment performance.
Variability in Biological Waste Treatment Systems
In the past, effluent requirements for wastewater treatment
plants have been related to the achievement of a desired
treatment efficiency based on long term performance.
The effluent limitations promulgated by EPA and developed in
this document include values that limit both long term and
short term waste discharges. These restrictions are
necessary to assure that deterioration of the nation's
waters does not occur on a short term basis due to heavy
133
-------
intermittent discharges, even though an annual average may
be attained.
Some of the controllable causes of variability and
techniques that can be used to minimize their effect
include:
A. Storm Runoff
Storm water holding or diversion facilities should be
designed on the basis of rainfall history and area being
drained. The collected storm runoff can be drawn off at a
constant rate to the treatment system. The volume of this
contaminated storm runoff should be minimized through
segregation and the prevention of contamination. Storm
runoff from outside the plant area, as well as
uncontaminated runoff, should be diverted around the plant
or contaminated area.
B. Flow Variations
Raw waste load variations can be reduced by properly sized
equalization units. Equalization is a retention of the
wastes in a suitably designed and operated holding system to
average out the influent before allowing it into the
treatment system.
C. Spills
Spills of certain materials in the plant can cause a heavy
loading on the treatment system for a short period of time.
A spill may not only cause higher effluent levels as it goes
through the system, but may inhibit a biological treatment
system and therefore have longer term effects. Equalization
helps to lessen the effects of spills. However, long term
reliable control can only be attained by an aggressive spill
prevention and maintenance program including training of
operating personnel. Industrial associations such as the
Manufacturing Chemists Association have developed guidelines
for prevention, control and reporting of spills. These note
how to assess the potential of spill occurrence and how to
prevent spills. If every plant were to use such guidelines
as part of plant waste management control programs, its raw
waste load and effluent variations would be decreased.
D. Climatic Effects
The design and choice of type of a treatment system should
be based on the climate at the plant location so that this
effect can be minimized. Where there are severe seasonal
134
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climatic conditions, the treatment system should be designed
and sufficient operational flexibility should be available
so that the system can function effectively under all
ambient conditions.
E. Treatment Process Inhibition
Chemicals likely to inhibit the treatment processes should
be identified and prudent measures taken to see that they do
not enter the wastewater in concentrations that may result
in treatment process inhibition. The common indicator of
the pollution characteristics of the discharge from a plant
historically has been the long-term average of the effluent
load. However, the long-term (yearly) average is not the
only parameter on which to have an effluent limitation.
Shorter term averages also are needed, both as an indication
of performance and for enforcement purposes.
Wherever possible, the best approach to develop the annual
and shorter term limitations is to use historical data from
the industry in question. If enough data is available from
a well designed and well operated plant, the shorter term
limitations can be developed from a detailed analysis of the
hourly, daily, weekly or monthly data. Rarely, however, is
there an adequate amount of short term data. However, using
data which show the variability in the effluent load,
statistical analyses can be used to compute short term
limits (30 day average or daily) which should be attained,
provided that the plant is adequately designed and operated
in the proper way to achieve the desired results. These
analyses can be used to establish variability factors for
effluent limitations or to check those factors that have
been developed.
Photographic Processing
It is apparent from the performance data collected on the
activated sludge unit during the field study that BOD5 and
COD reductions were variable during the first two years of
performance. Following the installation of the sand filters
in the second year, BOD5 reduction in percent brought about
by the combined installation varied from 78 percent to 91
percent; during a different period, COD reduction varied
from 45 percent to 70 percent. It is apparent that either
the system was improperly designed or improperly operated or
both.
The photographic processing subcategory is characterized by
batch-type operations, a very diverse product mix, and
seasonal production variation. As these process variations
135
-------
are similar to those in the pharmaceutical point source
category, the organic load variability on end-of-pipe
treatment plants for the photographic processing subcategory
and the pharmaceutical point source category are, therefore,
anticipated to be closely related. For the same reason, the
performance of end-of-pipe treatment plants in these two
categories should be similar. Consequently, the performance
factors of treatment plant operations as developed for the
pharmaceutical point source category from the long-term
performance of biological treatment plant operations could
be applied to the alternate biological systems considered
for the photographic processing subcategory also. These
performance factors are as follows:
TABLE XIII-1
Performance Factor Summary
Performance Factor Performance Factor
for Maximum Monthly for Maximum Daily
Parameter Effluent Value Effluent Value
BODS 2.1 2.9
COD 2.1 2.9
CN 1.0 2.0
Ag 1.0 2.0
TSS 2.1 2.9
As additional treatment plant performance data in this
subcategory becomes available, the above performance factors
will be reevaluated and modified, if necessary.
Sufficient historical data were not available from this
industry to perform a statistical analysis to determine
variability factors for silver and cyanide in treatment
plant effluent. The draft development document for effluent
limitations guidelines for the metal finishing industry
establishes a variability factor of 2.0 between the maximum
for any single day average and the thirty-day average.
Silver and cyanide numerical values for the maximum average
of daily values for any period of thirty consecutive days
(maximum thirty day limitation) and maximum value for any
one day (maximum day limitation) shown in Tables II-1 and
II-2 are developed using performance factors of 1.0 and 2.0
respectively.
136
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The performance factors presented in this section were
applied to the long-term average daily effluent limitations
to develop the effluent limitations, guidelines and new
source performance standards for the maximum thirty day
limitation and the maximum day limitation, as presented in
Sections II, IX, X, and XI of this document.
137
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SECTION XIV
ACKNOWLEDGEMENTS
This report was prepared by the Environmental Protection
Agency on the basis of a comprehensive study of this
industry performed by Roy F. Weston, Inc., under contract
No. 68-01-2932. The original study was conducted and
prepared for the Environmental Protection Agency under the
direction of Project Director James H. Dougherty, P.E., and
Technical Project Manager Jitendra R. Ghia, P.E. Update of
the original study was done by W.D. Sitman and Dr. K.M. Peil
of RFW, Inc.
The original RFW study and this EPA revision were conducted
under the supervision and guidance of Mr. Joseph S. Vitalis,
Project Officer, assisted by Mr. George Jett, Assistant
Project Officer.
Overall guidance and excellent assistance were provided the
Project Officer by his associates in the Effluent Guidelines
Division, particularly Messrs. Allen Cywin, Director, Ernst
P. Hall, Deputy Director, Walter J. Hunt, Branch Chief.
Special acknowledgement is also made of others in the
Effluent Guidelines Division: Messrs. John Nardella, Martin
Halper, David Becker, Bruno Maier, Dr. Chester Rhines and
Dr. Raymond Loehr, for their helpful suggestions and timely
comments. EGDB project personnel also wishes to acknowledge
the assistance of the personnel at the Environmental
Protection Agency's regional centers, who helped identify
those plants achieving effective waste treatment, and whose
efforts provided much of the research necessary for the
treatment technology review.
Appreciation is extended to Mr. James Rodgers of the EPA
Office of General Counsel for his valuable input.
The following individuals supplied input into the
development of this document while serving as members of the
EPA working group/steering committee which provided detailed
review, advice, and assistance:
W. Hunt, Chairman, Effluent Guidelines Development Branch,
Effluent Guidelines Division
L. Miller, Effluent Guidelines Division
J. Vitalis, Project Officer, Effluent Guidelines Div.
G. Jett, Asst. Project Officer, Effluent Guidelines Div.
J. Ciancia, NERC, Edison, New Jersey
M. Strier, Office of Enforcement
D. Davis, Office of Planning and Evaluation
C. Little, Office of General Counsel
139
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R. Swank, SERL, Athens, Georgia
E. Krabbe, Region II
L. Reading, Region VII
The National Association of Photographic Manufacturers,
Inc., (NAPM) are recognized for providing information used
in this document and for assisting in the selection of
representative photographic processing plants which provided
data relating to RWL and treatment plant performance.
The cooperation of the individual photographic processing
plants who offered their facilties for survey and
contributed pertinent data is gratefully appreciated.
Facilities visited were the property of the following:
Guardian Photo
Berkey Film Processing
Eastman Kodak Company
District Photo, Inc.
Furthermore, the Effluent Guidelines Development Branch
wishes to express appreciation to the following
organizations and individuals for the valuable assistance
which they provided throughout the study:
Thomas J. Dufficy, NAPM
Raymond M. Hertel, California Regional Water
Quality Board
J Roy King, Eastman Kodak Company
Irvin Kemp, U.S. Naval Photographic Center
Robert C. Ramsey, Eastman Kodak Company
Myron Rieser, District Photo, Inc.
William L. Button, M.D., Eastman Kodak Company
Donald Wilson, NERC Cincinnati
Paul A. Wilson, Eastman Kodak Company
Acknowledgement and appreciation is also given to Ms. Kay
Starr, Ms. Nancy Zrubek and Mr. Eric Yunker for invaluable
support in coordinating the preparation and reproduction of
this report, and to Mrs. Alice Thompson, Mrs. Ernestine
Christian, Ms. Laura Cammarota and Mrs. Carol Swann, of the
Effluent Guidelines Division secretarial staff for their
efforts in the typing of drafts, necessary revision, and
final preparation of the revised Effluent Guidelines
Division development document.
140
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SECTION XV
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152
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of Water and Hazardous Materials, Effluent
Guidelines Division, Washington, D.C. 20460;
December, 1975.
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SECTION XVI
GLOSSARY
G. Photographic Processing Industry
Black and White Film. This film consists of a support,
usually a plastic film which is coated with a light
sensitive emulsion and an outer protective layer. The
emulsion is adhered to the supporting base with a special
layer called a sub. The emulsion is made of: gelatin;
silver salts of bromide, iodide, and chloride; sensitizers;
hardeners; couplers; and emulsion plasticizers.
Bleaching. A step in color film processing whereby the
silver image which is formed with the dye image is converted
back to silver halide by reactions with ferricyanide and
sodium bromide or ferric EDTA.
Blix. A solution that contains both bleaching and fixing
chemicals used in some color processing to simultaneously
fix and bleach the processed material.
Complex Cyanide. This term refers to ferrocyanide
-*] and/or ferricyanide [ Fe (CM) 6>~ 3 ] .
Couplers. A group of organic chemicals which react with the
oxidized components of the developers to form color dyes.
They are either incorporated in the film emulsion at the
time of manufacture (e.g. , Ektachrome film) or they are
included in the color developing solution (e.g., Kodachrome
film) .
Developing Agents. These photographic materials usually are
aromatic compounds with phenolic or amino electron-donor
groups arranged ortho or para with respect to each other,
such as: hydroquinone, methyl p- amino- phenol (metol) , or 1-
phenol-3 pyrazolidone (phenidone) .
Development. A step in photoprocessing whereby the latent
image is made visible in a developer solution.
Developer Solution. This solution contains: (1) activators
like sodium or potassium carbonate, sodium hydroxide, borax,
phosphate; (2) preservatives like sodium sulfite,
hydroxylamine; (3) restrainers like sodium or potassium
bromide, sodium chloride, potassium iodide; (4) anti
foggants like benzotrizole; and (5) water conditioners like
phosphates, EDTA, or NCA.
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"Dip and Dunk". An automatic processing machine whereby
strips of film are "dipped" into successive photoprocessing
tanks and held for development.
Dye Image. A color image formed when the oxidized developer
combines with the color couplers.
EDTA. The disodium salt of ethylenediamine tetraacetic
acid. EDTA is oxidized well by ozonation.
Fix. A step in photoprocessing whereby the unexposed and
undeveloped silver must be removed from the emulsion.
Common among the solvent fixers are sodium thiosulfate.
Formalin. A 37.5 percent aqueous solution of formaldehyde
containing about 5 to 15 percent methanol. Dilute solutions
of formalin are readily biodegradable.
Glvcine. Aminoacetic acid. Glycine does not oxidize with
ozonation. Glycine is not to be confused with para-hydroxy-
phenyl glycine, commonly known as photographic-grade
glycine.
Hypo. The common name for the chemical compound sodium
thiosulfate which is a fixing agent.
Incorporated Couplers, couplers that are included in film
at the time of manufacture, common to reversal film.
Negative Film Development. A two-step process whereby,
following the negative development, a controlled exposure of
light is directed onto paper through the negative creating a
negative of a negative, or a positive image on paper.
Photochemical Reaction. A chemical reaction catalyzed by
light.
"Rack and Tank". See "Dip and Dunk".
Regeneration. The oxidation of ferrocyanide to
ferricyanide.
Reversal Development. A method of obtaining a positive
image on the same film used for the original exposure.
Short Stop. A step in photoprocessing which follows
development whereby the basic activators in the developer
are neutralized to prevent further development.
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Silver Halide. Usually silver bromide, which, upon exposure
to light converts to metallic silver, forming a latent
image.
Three Layers. Color film that has three separate chemical
layers that are sensitive to red, blue, and green light,
respectively.
Toxicity. The quality of being poisonous. The term toxic
or toxicity is used herein in the normal scientific sense of
the v word and not as a specialized term referring to section
307 (a) of the Act.
General Definitions
Abatement. The measures taken to reduce or eliminate
pollution.
Absorption. A process in which one material (the absorbent)
takes up and retains another (the absorbate) with the
formation of a homogeneous mixture having the attributes of
a solution. Chemical reaction may accompany or follow
absorption.
Acclimation. The ability of an organism to adapt to changes
in its immediate environment.
Acid. A substance which dissolves in water with the
formation of hydrogen ions.
Acid Solution. A solution with a pH of less than 7.00 in
which the activity of the hydrogen ion is greater than the
activity of the hydroxyl ion.
Acidity. The capacity of a wastewater for neutralizing a
base. It is normally associated with the presence of carbon
dioxide, mineral and organic acids and salts of strong acids
or weak bases. It is reported as equivalent of CaCO^
because many times it is not known just what acids are
present.
Acidulate. To make somewhat acidic.
Act. The Federal Water Pollution Control Act Amendments of
1972, Public Law 92-500.
Activated Carbon. Carbon which is treated by high-
temperature heating with steam or carbon dioxide producing
an internal porous particle structure.
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Activated Sludge Process. A process which removes the
organic matter from sewage by saturating it with air and
biologically active sludge. The recycle "activated"
microoganisms are able to remove both the soluble and
colloidal organic material from the wastewater.
Adsorption. An advanced method of treating wastes in which
a material removes organic matter not necessarily responsive
to clarification or biological treatment by adherence on the
surface of solid bodies.
Adsorption Isotherm. A plot used in evaluating the
effectiveness of activated carbon treatment by showing the
amount of impurity adsorbed versus the amount remaining.
They are determined at a constant temperature by varying the
amount of carbon used or the concentration of the impurity
in contact with the carbon.
Advance Waste Treatment. Any treatment method or process
employed following biological treatment to increase the
removal of pollution load, to remove substances that may be
deleterious to receiving waters or the environment or to
produce a high-quality effluent suitable for reuse in any
specific manner or for discharge under critical conditions.
The term tertiary treatment is commonly used to denote
advanced waste treatment methods.
Aeration. (1) The bringing about of intimate contact
between air and a liquid by one of the following methods:
spraying the liquid in the air, bubbling air through the
liquid, or agitation of the liquid to promote surface
absorption of air. (2) The process or state of being
supplied or impregnated with air; in waste treatment, a
process in which liquid from the primary clarifier is mixed
with compressed air and with biologically active sludge.
Aeration Period. (1) The theoretical time, usually
expressed in hours, that the mixed liquor is subjected to
aeration in an aeration tank undergoing activated-sludge
treatment. It is equal to the volume of the tank divided by
the volumetric rate of flow of wastes and return sludge.
(2) The theoretical time that liquids are subjected to
aeration.
Aeration Tank. A vessel for injecting air into the water.
Aerobic. Ability to live, grow, or take place only where
free oxygen is present.
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Aerobic Biological Oxidation. Any waste treatment or
process utilizing aerobic organisms, in the presence of air
or oxygen, as agents for reducing the pollution load or
oxygen demand of organic substances in waste.
Aerobic Digestion. A process in which microorganisms obtain
energy by endogenous or auto-oxidation of their cellular
protoplasm. The biologically degradable constituents of
cellular material are slowly oxidized to carbon dioxide,
water and ammonia, with the ammonia being further converted
into nitrates during the process.
Algae. One-celled or many-celled plants which grow in
sunlit waters and which are capable of photosynthesis. They
are a food for fish and small aquatic animals and, like all
plants, put oxygen in the water.
Algicide. Chemical agent used to destroy or control algae.
Alkali. A water-soluble metallic hydroxide that ionizes
strongly.
Alkalinity. The presence of salts of alkali metals. The
hydroxides, carbonates and bicarbonates of calcium, sodium
and magnesium are common impurities that cause alkalinity.
A quantitative measure of the capacity of liquids or
suspensions to neutralize strong acids or to resist the
establishment of acidic conditions. Alkalinity results from
the presence of bicarbonates, carbonates, hydroxides,
volatile acids, salts and occasionally borates and is
usually expressed in terms of the concentration of calcium
carbonate that would have an equivalent capacity to
neutralize strong acids.
Alum. A hydrated aluminum sulfate or potassium aluminum
sulfate or ammonium aluminum sulfate which is used as a
settling agent. A coagulant.
Ammonia Nitrogen. A gas released by the microbiological
decay of plant and animal proteins. When ammonia nitrogen
is found in waters, it is indicative of incomplete
treatment.
Ammonification. The process in which ammonia is liberated
from organic compounds by microoganisms.
Anaerobic. Ability to live, grow, or take place where there
is no air or free oxygen present.
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Anaerobic Biological Treatment. Any treatment method or
process utilizing anaerobic or facultative organisms, in the
absence of air, for the purpose of reducing the organic
matter in wastes or organic solids settled out from wastes.
Anaerobic Digestion. Biodegradable materials in primary and
excess activated sludge are stabilized by being oxidized to
carbon dioxide, methane and other inert products. The
primary digester serves mainly to reduce VSS, while the
secondary digester is mainly for solids-liquid separation,
sludge thickening and storage.
Anion. Ion with a negative charge.
Antagonistic Effect. The simultaneous action of separate
agents mutually opposing each other.
Aqueous Solution. One containing water or watery in nature.
Arithmetic Mean. The arithmetic mean of a number of items
is obtained by adding all the items together and dividing
the total by the number of items. It is frequently called
the average. It is greatly affected by extreme values.
Backwashing. The process of cleaning a rapid sand or
mechanical filter by reversing the flow of water.
Bacteria. Unicellular, plant-like microorganisms, lacking
chlorophyll. Any water supply contaminated by sewage is
certain to contain a bacterial group called "coliform".
Bateria, Coliform Groug. A group of bacteria, predominantly
inhabitants of the intestine of man but also found on
vegetation, including all aerobic and facultative anaerobic
gram-negative, non-sporeforming bacilli that ferment lactose
with gas formation. This group includes five tribes of
which the very great majority are Eschericheae. The
Eschericheae tribe comprises three genera and ten species,
of which Escherichia Coli and Aerobacter Aerogenes are
dominant. The Escherichia Coli are normal inhabitants of
the intestine of man and all vertbrates whereas Aerobacter
Aerogenes normally are found on grain and plants, and only
to a varying degree in the intestine of man and animals.
Formerly referred to as B. Coli, B. Coli group, and Coli-
Aerogenes Group.
Bacterial Growth. All bacteria require food for their
continued life and growth and all are affected by the
conditions of their environment. Like human beings, they
consume food, they respire, they need moisture, they require
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heat, and they give off waste products. Their food
requirements are very definite and have been, in general,
already outlined. Without an adequate food supply of the
type the specific organism requires, bacteria will not grow
and multiply at their maximum rate and they will therefore,
not perform their full and complete functions.
NSPS Effluent Limitations. Limitations for new sources
which are based on the application of the Best Available
Demonstrated Control Technology.
Base. A substance that in aqueous solution turns red litmus
blue, furnishes hydroxyl ions and reacts with an acid to
form a salt and water only.
Batch Process. A process which has an intermittent flow of
raw materials into the process and a resultant intermittent
flow of product from the process.
BAT Effluent Limitations. Limitations for point sources,
other than publicly owned treatment works, which are based
on the application of the Best Available Technology
Economically Achievable. These limitations must be achieved
by July 1, 1983.
Benthic. Attached to the bottom of a body of water.
Benthos. Organisms (fauna and flora) that live on the
bottoms of bodies of water.
Bioassay. An assessment which is made by using living
organisms as the sensors.
Biochemical Oxygen Demand (BOD). A measure of the oxygen
required to oxidize the organic material in a sample of
wastewater by natural biological process under standard
conditions. This test is presently universally accepted as
the yardstick of pollution and is utilized as a means to
determine the degree of treatment in a waste treatment
process. Usually given in mg/1 (or ppm units), meaning
milligrams of oxygen required per liter of wastewater, it
can also be expressed in pounds of total oxygen required per
wastewater or sludge batch. The standard BOD is five days
at 20 degrees C.
Biota. The flora and fauna (plant and animal life) of a
stream or other water body.
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Biological Treatment System. A system that uses
microorganisms to remove organic pollutant material from a
wastewater.
Slowdown. Water intentionally discharged from a cooling or
heating system to maintain the dissolved solids
concentration of the circulating water below a specific
critical level. The removal of a portion of any process
flow to maintain the constituents of the flow within desired
levels. Process may be intermittent or continuous. 2) The
water discharged from a boiler or cooling tower to dispose
of accumulated salts.
BODS. Biochemical Oxygen Demand (BOD) is the amount of
oxygen required by bacteria while stabilizing decomposable
organic matter under aerobic conditions. The BOD test has
been developed on the basis of a 5-day incubation period
(i.e. BODS).
BPT Effluent Limitations. Limitations for point sources,
other than publicly owned treatment works, which are based
on the application of the Best Practicable control
Technology Currently Available. These limitations must be
achieved by July 1, 1977.
Break Point. The point at which impurities first appear in
the effluent of a granular carbon adsorption bed.
Break Point Chlorination. The addition of sufficient
chlorine to destroy or oxidize all substances that creates a
chlorine demand with an excess amount remaining in the free
residual state.
Brine. Water saturated with a salt.
Buffer. A solution containing either a weak acid and its
salt or a weak base and its salt which thereby resists
changes in acidity or basicity, and resists changes in pH.
Carbonaceous. Containing or composed of carbon.
Catalyst. A substance which changes the rate of a chemical
reaction but undergoes no permanent chemical change itself.
Cation. The ion in an electrolyte which carries the
positive charge and which migrates toward the cathode under
the influence of a potential difference.
Caustic Soda. In its hydrated form it is called sodium
hydroxide. Soda ash is sodium carbonate.
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Centrate. The liquid fraction that is separated from the
solids fraction of a slurry through centrifugation.
Centrifugation. The process of separating heavier materials
from lighter ones through the employment of centrifugal
force.
Centrifuge. An apparatus that rotates at high speed and by
centrifugal force separates substances of different
densities.
Chemical Oxygen Demand (COD). A measure of oxygen-consuming
capacity of organic and inorganic matter present in water or
wastewater. It is expressed as the amount of oxygen
consumed from a chemical oxidant in a specific test. It
does not differentiate between stable and unstable organic
matter and thus does not correlate with biochemical oxygen
demand.
Chemical Synthes is. The processes of chemically combining
two or more constituent substances into a single substance.
Chlorination. The application of chlorine to water, sewage
or industrial wastes, generally for the purpose of
disinfection but frequently for accomplishing other
biological or chemical results.
Clarification. Process of removing turbidity and suspended
solids by settling. Chemicals can be added to improve and
speed up the settling process through coagulation.
Clarifier. A basin or tank in which a portion of the
material suspended in a wastewater is settled.
Clays. Aluminum silicates less than 0.002mm (2.0 urn) in
size. Therefore, most clay types can go into colloidal
suspension.
Coagulation. The clumping together of solids to make them
settle out of the sewage faster. Coagulation of solids is
brought about with the use of certain chemicals, such as
lime, alum or polyelectrolytes.
Coagulation and Flocculation. Processes which follow
sequentially.
Coagulation Chemicals. Hydrolyzable divalent and trivalent
metallic ions of aluminum, magnesium, and iron salts. They
include alum (aluminum sulfate), quicklime (calcium oxide),
hydrated lime (calcium hydroxide), sulfuric acid, anhydrous
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ferric chloride. Lime and acid affect only the solution pH
which in turn causes coagulant precipitation, such as that
of magnesium.
Coliform. Those bacteria which are most abundant in sewage
and in streams containing feces and other bodily waste
discharges. See bacteria, coliform group.
Colloid. A finely divided dispersion of one material (0.01-
10 micron-sized particles) , called the "dispersed phase"
(solid), in another material, called the "dispersion medium"
(liquid) .
Color Bodies. Those complex molecules which impart color to
a solution.
Color Units. A solution with the color of unity contains a
mg/1 of metallic platinum (added as potassium
chloroplatinate to distilled water). Color units are
defined against a platinum-cobalt standard and are based, as
are all the other water quality criteria, upon those
analytical methods described in Standard Methods for the
Examination of Water and Wastewater, 12 ed., Amer. Public
Health Assoc., N.Y., 1967.
Combined Sewer. One which carries both sewage and storm
water run-off.
Composite Sample. A combination of individual samples of
wastes taken at selected intervals, generally hourly for 24
hours, to minimize the effect of the variations in
individual samples. Individual samples making up the
composite may be of equal volume or be roughly apportioned
to the volume of flow of liquid at the time of sampling.
Composting. The biochemical stabilization of solid wastes
into a humus-like substance by producing and controlling an
optimum environment for the process,
Concentration. The total mass of the suspended or dissolved
particles contained in a unit volume at a given temperature
and pressure.
Conductivity. A reliable measurement of electrolyte
concentration in a water sample. The conductivity
measurement can be related to the concentration of dissolved
solids and is almost directly proportional to the ionic
concentration of the total electrolytes.
Contact Stabilization. Aerobic digestion.
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Contact Process Wastewaters. These are process-generated
wastewaters which have come in direct or indirect contact
with the reactants used in the process. These include such
streams as contact cooling water, filtrates, centrates, wash
waters, etc.
Continuous Process. A process which has a constant flow of
raw materials into the process and resultant constant flow
of product from the process.
Contract Disposal. Disposal of waste products through an
outside party for a fee.
Crustaceae. These are small animals ranging in size from
0.2 to 0.3 milimeters long which move very rapidly through
the water in search of food. They have recognizable head
and posterior sections. They form a principal source of
food for small fish and are found largely in relatively
fresh natural water.
Crystallization. The formation of solid particles within a
homogeneous phase. Formation of crystals separates a solute
from a solution and generally leaves impurities behind in
the mother liquid.
Culture^ A mass of microorganisms growing in a media.
Cyanide. Total cyanide as determined by the test procedure
specified in 40 CFP Part 136 (Federal Register, Vol. 38, no.
199, October 16, 1973).
Cyanide A. Cyanides amendable to chlorination as described
in "1972 Annual Book of ASTM Standards" 1972: Standard D
2036-72, Method B, p. 553.
Demineralization. The total removal of all ions.
Denitrification. Bacterial mediated reduction of nitrate to
nitrite. Other bacteria may act on the nitrite reducing it
to ammonia and finally N2 gas. This reduction of nitrate
occurs under anaerobic conditions. The nitrate replaces
oxygen as an electron acceptor during the metabolism of
carbon compounds under anaerobic conditions. A biological
process in which gaseous nitrogen is produced from nitrite
and nitrate. The heterotrophic microoganisms which
participate in this process include pseudomonades,
achromobacters and bacilli.
Derivative. A substance extracted from another body or
substance.
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Desorption. The opposite of adsorption. A phenomenon where
an adsorbed molecule leaves the surface of the adsorbent.
Diluent. A diluting agent.
Disinfection. The process of killing the larger portion
(but not necessarily all) of the harmful and objectionable
microorganisms in or on a medium.
Dissolved Air Flotation. The term "flotation" indicates
something floated on or at the surface of a liquid.
Dissolved air flotation thickening is a process that adds
energy in the form of air bubbles, which become attached to
suspended sludge particles, increasing the buoyancy of the
particles and producing more positive flotation.
Dissolved Oxygen (DO). The oxygen dissolved in sewage,
water or other liquids, usually expressed either in
milligrams per liter or percent of saturation. It is the
test used in BOD determination.
Distillation. The separation, by vaporization, of a liquid
mixture of miscible and volatile substance into individual
components, or, in some cases, into a group of components.
The process of raising the temperature of a liquid to the
boiling point and condensing the resultant vapor to liquid
form by cooling. It is used to remove substances from a
liquid or to obtain a pure liquid from one which contains
impurities or which is a mixture of several liquids having
different boiling temperatures. Used in the treatment of
fermentation products, yeast, etc., and other wastes to
remove recoverable products.
DO Units. The units of measurement used are milligrams per
liter (mg/1) and parts per million (ppm), where mg/1 is
defined as the actual weight of oxygen per liter of water
and ppm is defined as the parts actual weight of oxygen
dissolved in a million parts weight of water, i.e., a pound
of oxygen in a million pounds of water is 1 ppm. For
practical purposes in pollution control work, these two are
used interchangeably; the density of water is so close to 1
g/cm3 that the error is negligible. Similarly, the changes
in volume of oxygen with changes in temperature are
insignificant. This, however, is not true if sensors are
calibrated in percent saturation rather than in mg/1 or ppm.
In that case, both temperature and barometric pressure must
be taken into consideration.
Dual Media. A deep-bed filtration system utilizing two
separate and discrete layers of dissimilar media (e.g..
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anthracite and sand) placed one on top of the other to
perform the filtration function.
Ecology. The s.cience of the interrelations between living
organisms and their environment.
Effluent. A liquid which leaves a unit operation or
process. Sewage, water or other liquids, partially or
completely treated or in their natural states, flowing out
of a reservoir basin, treatment plant or any other unit
operation. An influent is the incoming stream.
Elution. (1) The process of washing out, or removing with
the use of a solvent. (2) In an ion exchange process it is
defined as the stripping of adsorbed ions from an ion
exchange resin by passing through the resin solutions
containing other ions in relatively high concentrations.
Elutriation. A process of sludge conditioning whereby the
sludge is washed, either with fresh water or plant effluent,
to reduce the sludge alkalinity and fine particles, thus
decreasing the amount of required coagulant in further
treatment steps, or in sludge dewatering.
Emulsion. Emulsion is a suspension of fine droplets of one
liquid in another.
Environment. The sum of all external influences and
conditions affecting the life and the development of an
organism.
Equalization Basin. A holding basin in which variations in
flow and composition of a liquid are averaged. Such basins
are used to provide a flow of reasonably uniform volume and
composition to a treatment unit.
Eutrophication. The process in which the life-sustaining
quality of a body of water is lost or diminished (e.g.,
aging or filling in of lakes). A eutrophic condition is one
in which the water is rich in nutrients but has a seasonal
oxygen deficiency.
Evapotranspiration. The loss of water from the soil both by
evaporation and by transpiration from the plants growing
thereon.
Facultative. Having the power to live under different
conditons (either with or without oxygen).
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Facultative Lagoon. A combination of the aerobic and
anaerobic lagoons. It is divided by loading and thermal
stratifications into an aerobic surface and an anaerobic
bottom, therefore the principles of both the aerobic and
anaerobic processes apply.
Fauna. The animal life adapted for living in a specified
environment.
Fermentation. Oxidative decomposition of complex substances
through the action of enzymes or ferments produced by
mi croo rgan i sm s.
Filter, Trickling. A filter consisting of an artificial bed
of coarse material, such as broken stone, clinkers, slate,
slats or brush, over which sewage is distributed and applied
in drops, films or spray, from troughs, drippers, moving
distributors or fixed nozzles. The sewage trickles through
to the underdrains and has the opportunity to form zoogleal
slimes which clarify and oxidize the sewage.
Filter, Vacuum. A filter consisting of a cylindrical drum
mounted on a horizontal axis and covered with a filter
cloth. The filter revolves with a partial submergence in
the liquid, and a vacuum is maintained under the cloth for
the larger part of each revolution to extract moisture. The
cake is scraped off continuously.
Filtrate. The liquid fraction that is separated from the
solids fraction of a slurry through filtration.
Filtration, Biological. The process of passing a liquid
through a biological filter containing media on the surfaces
of which zoogleal films develop that absorb and adsorb fine
suspended, colloidal and dissolved solids and that release
various biochemical end products.
Flocculants. Those water-soluble organic polyelectrolytes
that are used alone or in conjunction with inorganic
coagulants such as lime, alum or ferric chloride or
coagulant aids to agglomerate solids suspended in aqueous
systems or both. The large dense floes resulting from this
process permit more rapid and more efficient solids-liquid
separations.
Flocculation. The formation of floes. The process step
following the coagulation-precipitation reactions which
consists of bringing together the colloidal particles. It
is the agglomeration by organic polyelectroytes of the
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small, slowly settling floes formed during coagulation into
large floes which settle rapidly.
Flora. The plant life characteristic of a region.
Flotation. A method of raising suspended matter to the
surface of the liquid in a tank as scum-by aeration, vacuum,
evolution of gas, chemicals, electrolysis, heat or bacterial
decomposition and the .subsequent removal of the scum by
skimming.
Fungus. A vegetable cellular organism that subsists on
organic material, such as bacteria.
Gland. A device utilizing a soft wear-resistant material
used to minimize leakage between a rotating shaft and the
stationary portion of a vessel such as a pump.
Gland Water. Water used to lubricate a gland. Sometimes
called "packing water."
Grab Sample. (1) Instantaneous sampling. (2) A sample
taken at a random place in space and time.
Grease. In sewage, grease includes fats, waxes, free fatty
acids, calcium and magnesium soaps, mineral oils and other
nonfatty materials. The type of solvent to be used for its
extraction should be stated.
Grit Chamber. A small detention chamber or an enlargement
of a sewer designed to reduce the velocity of flow of the
liquid and permit the separation of mineral from organic
solids by differential sedimentation.
Groundwater. The body of water that is retained in the
saturated zone which tends to move by hydraulic gradient to
lower levels.
Hardness. A measure of the capacity of water for
precipitating soap. It is reported as the hardness that
would be produced if a certain amount of CaCC3 were
dissolved in water. More than one ion contributes to water
hardness. The "Glossary of Water and Wastewater Control
Engineering" defines hardness as: A characteristic of water,
imparted by salts of calcium, magnesium, and ions, such as
bicarbonates, carbonates, sulfates, chlorides, and nitrates,
that cause curdling of soap, deposition of scale in boilers,
damage in some industrial process, and sometimes
objectionable taste. Calcium and magnesium are the most
significant constituents.
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Metals. A general name given for the ions of metallic
elements, such as copper, zinc, iron, chromium, and
aluminum. They are normally removed from a wastewater by
the formation of an insoluble precipitate (usually a
metallic hydroxide).
Hydrocarbon. A compound containing only carbon and
hydrogen.
Hydrolysis. A chemical reaction in which water reacts with
another substance to form one or more new substances.
Incineration. The combustion (by burning) of organic matter
in wastewater sludge.
Incubate. To maintain cultures, bacteria, or other
microorganisms at the most favorable temperature for
development.
Influent. Any sewage, water or other liquid, either raw or
partly treated, flowing into a reservoir, basin, treatment
plant, or any part thereof. The influent is the stream
entering a unit operation; the effluent is the stream
leaving it.
In-Plant Measures. Technology applied within the
manufacturing process to reduce or eliminate pollutants in
the raw waste water. Sometimes called "internal measures"
or "internal controls".
Ion. An atom or group of atoms possessing an electrical
charge.
Ion Exchange. A reversible interchange of ions between a
liquid and a solid involving no radical change in the
structure of the solid. The solid can be a natural zeolite
or a synthetic resin, also called polyelectrolyte. Cation
exchange resins exchange their hydrogen ions for metal
cations in the liquid. Anion exchange resins exchange their
hydroxyl ions for anions such as nitrates in the liquid.
When the ion-retaining capacity of the resin is exhausted,
it must be regenerated. Cation resins are regenerated with
acids and anion resins with bases.
Lacrimal. Tear forming fluid.
Lagoons. An oxidation pond that receives sewage which is
not settled or biologically treated.
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LC 50. A lethal concentration for 505? of test animals.
Numerically the same as TLm. A statistical estimate of the
toxicant, such as pesticide concentration, in water
necessary to kill 50% of the test organisms within a
specified time under standardized conditions (usually 24,48
or 96 hr) .
Leach. To dissolve out by the action of a percolating
liquid, such as water, seeping through a sanitary landfill.
Lime. Limestone is an accumulation of organic remains
consisting mostly of calcium carbonate. When burned, it
yields lime which is a solid. The hydrated form of a
chemical lime is calcium hydroxide.
Liquid-licruid-ex traction. The process by which the
constituents of a solution are separated by causing their
unegual distribution between two insoluble liquids.
Maximum Day Limitation. The effluent limitation value equal
to the maximum for any one day and is the value to be
published by EPA in the Federal Register.
Maximum Thirty Day Limitation. The effluent limitation
value for which the average of daily values for thirty
consecutive days shall not exceed and is the value to be
published by EPA in the Federal Register.
Mean. The arithmetic average of the individual sample
values.
Median. In a statistical array, the value having as many
cases larger in value as cases smaller in value.
Median Lethal Dose (LD50) . The dose lethal to 50 percent of
a group of test organisms for a specified period. The dose
material may be ingested or injected.
Median Tolerance Limit (TLm). In toxicological studies, the
concentration of pollutants at which 50 percent of the test
animals can survive for a specified period of exposure.
Microbjal. Of or pertaining to a pathogenic bacterium.
Mixed Liquor. The mixture of recirculated activated sludge
and primary clarifier overflow which enters the aeration
tank.
Mixed Liquor Suspended Solids jMLSS). This is a vital
design factor for conventional activated sludge systems and
171
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is used to define sludge retention time (SRT). SRT equals
pounds of MLSS under aeration divided by the pounds of
suspended solids wasted and pounds of suspended solids lost
in final effluent per day.
Molecular Weight. The relative weight of a molecule
compared to the weight of an atom of carbon taken as exactly
12.00; the sum of the atomic weights of the atoms in a
molecule.
MoHusk (mollusca). A large animal group including those
forms popularly called shellfish (but not including
crustaceans). All have a soft unsegmented body protected in
most instances by a calcareous shell. Examples are snails,
mussels, clams, and oysters.
Mycelium. The mass of filaments which constitutes the
vegetative body of fungi.
Navigable Waters. Includes all navigable waters of the
United States; tributaries of navigable waters; interstate
waters; intrastate lakes, rivers and streams which are
utilized by interstate travellers for recreational or other
purposes; intrastate lakes, rivers and streams from which
fish or shellfish are taken and sold in interstate commerce;
and intrastate lakes, rivers and streams which are utilized
for industrial purposes by industries in interstate
commerce.
Neutralization. The restoration of the hydrogen or
hydroxyl ion balance in a solution so that the ionic
concentration of each are equal. Conventionally, the
notation "pH" (puissance d1hydrogen) is used to describe the
hydrogen ion concentration or activity present in a given
solution. For dilute solutions of strong acids, i.e., acids
which are considered to be completely dissociated (ionized
in solution), activity equals concentration.
New Source. Any facility from which there is or may be a
discharge of pollutants, the construction of which is
commenced after the publication of proposed regulations
prescribing a standard of performance under section 306 of
the Act.
Nitrate Nitrogen. The final decomposition product of the
organic nitrogen compounds. Determination of this parameter
indicates the degree of waste treatment.
Nitrification. Bacterial mediated oxidation of ammonia to
nitrite. Nitrite can be further oxidized to nitrate. These
172
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reactions are brought about by only a few specialized
bacterial species. Nitrosomonias sp. and Nitrococcus sp.
oxidize ammonia to nitrite which is oxidized to nitrate by
Nitrobacter sp.
«
Nitrifiers. Bacteria which causes the oxidation of ammonia
to nitrites and nitrates.
Nitrite Nitrogen. An intermediate stage in the decompo-
sition of organic nitrogen to the nitrate form. Tests for
nitrite nitrogen can determine whether the applied treatment
is sufficient.
Nitrobacteria. Those bacteria (an autotrophic genus) that
oxidize nitrite nitrogen to nitrate nitrogen.
Nitrogen Cycle. Organic nitrogen in waste is oxidized by
bacteria into ammonia. If oxygen is present, ammonia is
bacterially oxidized first into nitrite and then into
nitrate. If oxygen is not present, nitrite and nitrate are
bacterially reduced to nitrogen gas. The second step is
called "denitrification."
Nitrogen Fixation. Biological nitrogen fixation is carried
on by a selected group of bacteria which take up atmospheric
nitrogen and convert it to amine groups or for amino acid
synthesis.
Nitrosomonas. Bacteria which oxidize ammonia nitrogen into
nitrite nitrogen; an aerobic autotrophic life form.
Non-contact Cooling Water. Water used for cooling that does
not come into direct contact with any raw material,
intermediate product, waste product or finished product.
Non-contadt Process Wastewaters. Wastewaters generated by a
manufacturing process which have not come in direct contact
with the reactants used in the process. These include such
streams as non-contact cooling water, cooling tower
blowdown, boiler blowdown, etc.
Nonputresci ble. Incapable of organic decomposition or
decay.
Normal Solution. A solution that contains 1 gm molecular
weight of the dissolved substance divided by the hydrogen
equivalent of the substance (that is, one gram equivalent)
per liter of solution. Thus, a one normal solution of
sulfuric acid (H2S
-------
NPDES. National Pollution Discharge Elimination System. A
federal program requiring industry to obtain permits to
discharge plant effluents to the nation's water courses.
Nutrient. Any substance assimilated by an organism which
promotes growth and replacement of cellular constituents.
Operations and Maintenance. Costs required to operate and
maintain pollution abatement equipment including labor,
material, insurance, taxes, solid waste disposal, etc.
Organic Loading. In the activated sludge process, the food
to micoorganisms (F/M) ratio defined as the amount of
biodegradable material available to a given amount of
microorganisms per unit of time.
Osmosis. The diffusion of a solvent through a semipermeable
membrane into a more concentrated solution.
Oxidation. A process in which an atom or group of atoms
loses electrons; the combination of a substance with oxygen,
accompanied with the release of energy. The oxidized atom
usually becomes a positive ion while the oxidizing agent
becomes a negative ion in (chlorination for example).
Oxidation Pond. A man-made lake or body of water in which
wastes are consumed by bacteria. It receives an influent
which has gone through primary treatment while a lagoon
receives raw untreated sewage.
Oxidation Reduction (OR). A class of chemical reactions in
which one of the reacting species gives up electrons
(oxidation) while another species in the reaction accepts
electrons (reduction). At one time, the term oxidation was
restricted to reactions involving hydrogen. Current
chemical technology has broadened the scope of these terms
to include all reactions where electrons are given up and
taken on by reacting species; in fact, the donating and
accepting of electrons must take place simultaneously.
Oxygen, Available. The quantity of atmospheric oxygen
dissolved in the water of a stream; the quantity of
dissolved oxygen available for the oxidation of organic
matter in sewage.
Oxygen, Dissolved. The oxygen (usually designated as DO)
dissolved in sewage, water or another liquid and usually
expressed in parts per million or percent of saturation.
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Ozonation. A water or wastewater treatment process
involving the use of ozone as an oxidation agent.
Ozone. That molecular oxygen with three atoms of oxygen
forming each molecule. The third atom of oxygen in each
molecule of ozone is loosely bound and easily released.
Ozone is used sometimes for the disinfection of water but
more frequently for the oxidation of taste-producing
substances, such a.s phenol, in water a*nd for the
neutralization of odors in gases or air.
Parameter. A variable whose measurement aids in
characterizing the sample.
Parts Per Million (ppm). Parts by weight in sewage
analysis; ppm by weight is equal to milligrams per liter
divided by the specific gravity. It should be noted that in
water analysis ppm is always understood to imply a
weight/weight ratio, even though in practice a volume may be
measured instead of a weight.
Pathogenic. Disease producing.
Percolation. The movement of water beneath the ground
surface both vertically and horizontally, but above the
groundwater table.
Permeability. The ability of a substance (soil) to allow
appreciable movement of water through it when saturated and
actuated by a hydrostatic pressure.
pH. The negative logarithm of the hydrogen ion
concentration or activity in a solution. The number 7
indicates neutrality, numbers less than 7 indicate
increasing acidity, and numbers greater than 7 indicate
increasing alkalinity.
Phenol. Class of cyclic organic derivatives with the basic
chemical formula C6H5OH.
Phosphate. Phosphate ions exist as an ester or salt of
phosphoric acid, such as calcium phosphate rock. In
municipal wastewater, it is most frequently present as
orthophosphate.
Phosphorus Precipitation. The addition of the multivalent
metallic ions of calcium, iron and aluminum to wastewater to
form insoluble precipitates with phosphorus.
175
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Photosynthesis. The mechanism by which chlorophyll-bearing
plants utilize light energy to produce carbohydrate and
oxygen from carbon dioxide and water (the reverse of
respiration).
Physical/Chemical Treatment System. A system that utilizes
physical (i.e., sedimentation, filtration, centrifugation,
activated carbon, reverse osmosis, etc.) and/or chemical
means (i.e., coagulation, oxidation, precipitation, etc.) to
treat wastewaters.
Phytoplankton. (1) Collective term for the plants and plant
like organisms present in plankton; contrasts with zoo-
plankton.
Plankton. Collective term for the passively floating or
drifting flora and fauna of a body of water; consists
largely of microscopic organisms.
Point Source. Any discernible, confined and discrete
conveyance, including but not limited to any pipe, ditch,
channel, tunnel, conduit, well, discrete fissure, container,
rolling stock, concentrated animal feeding operation, or
vessel or other floating craft, from which pollutants are or
may be discharged.
Pollutional Load. A measure of the strength of a wastewater
in terms of its solids or oxygen-demanding characteristics
or other objectionable physical and chemical characteristics
or both or in terms of harm done to receiving waters. The
pollutional load imposed on sewage treatment works is
expressed as population equivalent.
Polyelectrolytes. Synthetic chemicals (polymers) used to
speed up the removal of solids from sewage. These chemicals
cause solids to coagulate or clump together more rapidly
than do chemicals such as alum or lime. They can be anionic
(-charge) , nonionic (+ and -charge) or cationic (^charge—
the most popular). They are linear or branched organic
polymers. They have high molecular weights and are water-
soluble. Compounds similar to the polyelectrolyte
flocculants include surface-active agents and ion exchange
resins. The former are low molecular weight, water soluble
compounds used to disperse solids in aqueous systems. The
latter are high molecular weight, water-insoluble compounds
used to selectively replace certain ions already present in
water with more desirable or less noxious ions.
Population Equivalent (PE). An expression of the relative
strength of a waste (usually industrial) in terms of its
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equivalent in domestic waste, expressed as the population
that would produce the equivalent domestic waste. A
population equivalent of 160 million persons means the
pollutional effect equivalent to raw sewage from 160 million
persons; 0.17 pounds BOD (the oxygen demand of untreated
wastes from one person) = 1 PE.
Potable Water. Drinking water sufficiently pure for human
use.
Potash. Potassium compounds used in agriculture and
industry. Potassium carbonate can be obtained from wood
ashes. The mineral potash is usually a muriate. Caustic
potash is its hydrated form.
Preaeration . A preparatory treatment of sewage consisting
of aeration to remove gases and add oxygen or to promote the
flotation of grease and aid coagulation.
Precipitation. The phenomenon which occurs when a substance
held in solution passes out of that solution into solid
form. The adjustment of pH can reduce solubility and cause
precipitation. Alum and lime are frequently used chemicals
in such operations as water softening or alkalinity
reduction.
Pretreatment. Any wastewater treatment process used to
partially reduce the pollution load before the wastewater is
introduced into a main sewer system or delivered to a
treatment plant for substantial reduction of the pollution
load.
Primary Clarifier. The settling tank into which the
wastewater (sewage) first enters and from which the solids
are removed as raw sludge.
Primary Sludge. Sludge from primary clarifiers.
Primary Treatment. The removal of material that floats or
will settle in sewage by using screens to catch the floating
objects and tanks for the heavy matter to settle in. The
first major treatment and sometimes the only treatment in a
waste-treatment works, usually sedimentation and/or
flocculation and digestion. The removal of a moderate
percentage of suspended matter but little or no colloidal or
dissolved matter. It may effect the removal of 30 to 35
percent or more BOD.
Process Waste Water. Any water which, during manufacturing
or processing, comes into direct contact with or results
177
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from the production or use of any raw material, intermediate
product, finished product, by-product, or waste product.
Process Water. Any water (solid, liquid or vapor) which,
during the manufacturing process, comes into direct contact
with any raw material, intermediate product, by-product,
waste product, or finished product.
Putrefaction. Biological decomposition of organic matter
accompanied by the production of foul-smelling products
associated with anaerobic conditions.
Pyrolysis. The high temperature decomposition of complex
molecules that occurs in the presence of an inert atmosphere
(no oxygen present to support combustion).
Raw Waste Load (RWL). The quantity (kg) of pollutant being
discharged in a plant's wastewater. measured in terms of
some common denominator (i.e., kkg of production or m2 of
floor area).
Receiving waters. Rivers, lakes, oceans or other courses
that receive treated or untreated wastewaters.
Recirculation. The refiltration of either all or a portion
of the effluent in a high-rate trickling filter for the
purpose of maintaining a uniform high rate through the
filter. (2) The return of effluent to the incoming flow to
reduce its strength.
Reduction. A process in which an atom (or group of atoms)
gain electrons. Such a process always requires the input of
energy.
Refractory Organics. Organic materials that are only
partially degraded or entirely nonbiodegradable in
biological waste treatment processes. Refractory organics
include detergents, pesticides, color- and odor-causing
agents, tannins, lignins, ethers, olefins, alcohols, amines,
aldehydes, ketones, etc.
Residual Chlorine. The amount of chlorine left in the
treated water that is available to oxidize contaminants if
they enter the stream. It is usually in the form of
hypochlorous acid of hypochlorite ion or of one of the
chloramines. Hypochlorite concentration alone is called
"free chlorine residual" while together with the chloramine
concentration their sum is called "combined chlorine
residual."
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Respiration. Biological oxidation within a life form; the
most likely energy source for animals (the reverse of
photosynthesis).
•
Retention Time. Volume of the vessel divided by the flow
rate through the vessel.
Reverse Osmosis. The process in which a solution is
pressurized to a degree greater than the osmotic pressure of
the solvent, causing it to pass through a membrane.
Salt. A compound made up of the positive ion of a base and
the negative ion of an acid.
Sanitary Landfill. A sanitary landfill is a land disposal
site employing an engineered method of disposing of solid
wastes on land in a manner that minimizes environmental
hazards by spreading the wastes in thin layers, compacting
the solid wastes to the smallest practical volume, and
applying cover material at the end of each operating day.
There are two basic sanitary landfill methods; trench fill
and area or ramp fill. The method chosen is dependent on
many factors such as drainage and type of soil at the
proposed landfill site.
Sanitary Sewers. In a separate system, pipes in a city that
carry only domestic wastewater. The storm water runoff is
handled by a separate system of pipes.
Screening. The removal of relatively coarse, floating and
suspended solids by straining through racks or screens.
Secondary Treatment. The second step in most waste
treatment systems in which bacteria consume the organic part
of the wastes. This is accomplished by bringing the sewage
and bacteria together either in trickling filters or in the
activated sludge process.
Sedimentation, Final. The settling of partly settled,
flocculated or oxidized sewage in a final tank. (The term
settling is preferred).
Sedimentation, Plain. The sedimentation of suspended matter
in a liquid unaided by chemicals or other special means and
without any provision for the decomposition of the deposited
solids in contact with the sewage. (The term plain settling
is preferred).
Seed. To introduce microorganisms into a culture medium.
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Settleable Solids. Suspended solids which will settle out
of a liquid waste in a given period of time.
Settling Velocity. The terminal rate of fall of a particle
through a fluid as induced by gravity or other external
forces.
Sewage, Raw. Untreated sewage.
Sewage, Storm. The liquid flowing in sewers during or
following a period of heavy rainfall and resulting
therefrom.
Sewerage. A comprehensive term which includes facilities
for collecting, pumping, treating, and disposing of sewage;
the sewerage system and the sewage treatment works.
Silt. Particles with a size distribution of 0.05mm-0.002mm
(2.0um). Silt is high in quartz and feldspar.
Skimming. Removing floating solids (scum) .
Sludger Activated. Sludge floe produced in raw or settled
sewage by the growth of zoogleal bacteria and other
organisms in the presence of dissolved oxygen and
accumulated in sufficient concentration by returning the
floe previously formed.
Sludge, Age. The ratio of the weight of volatile solids in
the digester to the weight of volatile solids added per day.
There is a maximum sludge age beyond which no significant
reduction in the concentration of volatile solids will
occur.
Sludge, Digested. Sludge digested under anaerobic
conditions until the volatile content has been reduced,
usually by approximately 50 percent or more.
Solution. A homogeneous mixture of two or more substances
of dissimilar molecular structure. In a solution, there is
a dissolving medium-solvent and a dissolved substance-
solute.
Solvent. A liquid which reacts with a material, bringing it
into solution.
Solvent Extraction. A mixture of two components is treated
by a solvent that preferentially dissolves one or more of
the components in the mixture. The solvent in the extract
leaving the extractor is usually recovered and reused.
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Sparger. An air diffuser designed to give large bubbles,
used singly or in combination with mechanical aeration
devices.
Standard Deviation. The square root of the variance which
describes the variability within the sampling data on the
basis of the deviation of individual sample values from the
mean.
Standard Raw Waste Load (SRWL). The raw waste load which
characterizes a specific subcategory. This is generally
computed by averaging the plant raw waste loads within a
subcategory.
Sterilization. The complete destuction of all living
organisms in or on a medium; heat to 121°C at 5 psig for 15
minutes.
Stillwell. A pipe, chamber, or compartment with
comparatively small inlet or inlets communicating with a
main body of water. Its purpose is to dampen waves or
surges while permitting the water level within the well to
rise and fall with the major fluctuations of the main body
of water. It is used with water-measuring devices to
improve accuracy of measurement.
Stoichiometric. Characterized by being a proportion of
substances exactly right for a specific chemical reaction
with no excess of any reactant or product.
Substrate. (1) Peactant portion of any biochemical
reaction, material transformed into a product. (2) Any
substance used as a nutrient by a microorganism. (3) The
liquor in which activated sludge or other material is kept
in suspension.
Sulfate. The final decomposition product of organic sulfur
compounds.
Supernatant. Floating above or on the surface.
Surge tank. A tank for absorbing and dampening the wavelike
motion of a volume of liquid; an in-process storage tank
that acts as a flow buffer between process tanks.
Suspended Solids. The wastes that will not sink or settle
in sewage. The quantity of material deposited on a filter
when a liquid is drawn through a Gooch crucible.
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Synerqistic. An effect which is more than the sum of the
individual contributors.
Svnergistic Effect. The simultaneous action of separate
agents which, together, have greater total effect than the
sum of their individual effects.
Tertiary Treatment. A process to remove practically all
solids and organic matter from wastewater. Granular
activated carbon filtration is a tertiary treatment process.
Phosphate removal by chemical coagulation is also regarded
as a step in tertiary treatment.
Thermal Oxidation. The wet combustion of organic materials
through the application of heat in the presence of oxygen.
TKN (Total K-jeldahl Nitrogen) . Includes ammonia and organic
nitrogen but does not include nitrite and nitrate nitrogen.
The sum of free nitrogen and organic nitrogen in a sample.
TLm. The concentration that kills 50% of the test organisms
within a specified time span, usually in 96 hours or less.
Most of the available toxicity data are reported as the
median tolerance limit (TLm). This system of reporting has
been misapplied by some who have erroneously inferred that a
TLm value is a safe value, whereas it is merely the level at
which half of the test organisms are killed. In many cases,
the differences are great between TLm concentrations and
concentrations that are low enough to permit reproduction
and growth. LC50 has the same numerical value as TLm.
Total Organic Carbon (TOC). A measure of the amount of
carbon in a sample originating from organic matter only.
The test is run by burning the sample and measuring the
carbon dioxide produced.
Total Solids. The total amount of solids in a wastewater
both in solution and suspension.
Total Volatile Solids (TVS). The quantity of residue lost
after the ignition of total solids.
Transport Water. Water used to carry insoluble solids.
Trickling Filter. A bed of rocks or stones. The sewage is
trickled over the bed so that bacteria can break down the
organic wastes. The bacteria collect on the stones through
repeated use of the filter.
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Turbidity. A measure of the amount of solids in suspension.
The units of measurement are parts per million (ppm) of
suspended solids or Jackson Candle Units. The Jackson
Candle Unit (JCU) is defined as the turbidity resulting from
1 ppm of fuller's earth (and inert mineral) suspended in
water. The relationship between ppm and JCU depends on
particle size, color, index of refraction; the correlation
between the two is generally not possible. Turbidity
instruments utilize a light beam projected into the sample
fluid to effect a measurement. The light beam is scattered
by solids in suspension, and the degree of light attenuation
or the amount of scattered light can be related to
turbidity. The light scattering is called the Tyndall
effect and the scattered light the Tyndall light. An
expression of the optical property of a sample which causes
light to be scattered and absorbed rather than transmitted
in straight lines through the sample.
Volatile Suspended Solids (VSS). The quantity of suspended
solids lost after the ignition of total suspended solids.
Waste Treatment Plant. A series of tanks, screens, filters,
pumps and other equipment by which pollutants are removed
from water.
Water Quality Criteria. Those specific values of water
quality associated with an identified beneficial use of the
water under consideration.
Weir. A flow measuring device consisting of a barrier
across an open channel, causing the liquid to flow over its
crest. The height of the liquid above the crest varies with
the volume of liquid flow.
Wet Air Pollution Control. The technique of air pollution
abatement utilizing water as an absorptive media.
Wet Oxidation. The direct oxidation of organic matter in
wastewater liquids in the presence of air under heat and
pressure; generally applied to organic matter oxidation in
sludge.
Zeolite. Various natural or synthesized silicates used in
water softening and as absorbents.
Zooplankton. (1) The animal portion of the plankton. (2)
Collective term for the nonphotosynthetic organisms present
in plankton; contrasts with phytoplantkton.
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SECTION XVII
ABBREVIATIONS AND SYMBOLS
A.C. activated
ac ft acre-foot
Ag. silver
atm atmosphere
ave average
B, boron
Ba. barium
bbl barrel
BOD5 biochemical oxygen demand, five day
Btu British thermal unit
C centigrade degrees
C.A. carbon adsorption
cal calorie
cc cubic centimeter
cfm cubic foot per minute
cfs cubic foot per second
Cl. chloride
cm centimeter
CN cyanide
COD chemical oxygen demand
cone. Concentration
cu cubic
db decibels
deg degree
CO dissolved oxygen
E. Coli. Escherichia coliform bacteria
Eq. equation
F Fahrenheit degrees
Fig. figure
F/M BOD5 (Wastewater flow)/ MLSS (contractor volume)
fpm foot per minute
fps foot per second
ft foot
g gram
gal gallon
gpd gallon per day
gpm gallon per minute
Hg. mercury
hp horsepower
hp-hr horsepower-hour
hr hour
in. inch
kg kilogram
kw kilowatt
kwhr kilowatt-hour
185
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L(l)
L/kkg
Ib
m
M
me
mg
mgd
min
ml
MLSS
MLVSS
MM
mole
mph
MPN
mu
N0.3
NH3_-N
02_
P04_
p.
pH
pp.
ppb
ppm
psf
psi
psig
R.O.
rpm
RWL
sec
Sec.
S.I.C.
SOx
sq
sq ft
SS
stp
SRWL
TDS
TKN
TLm
TOG
TOD
TSS
u
ug
vol
wt
yd
liter
liters per 1000 kilograms
pound
meter
thousand
milliequivalent
milligram
million gallons daily
minute
milliliter
mixed-liquor suspended solids
mixed-liquor volatile suspended solids
million
gram-molecular weight
mile per hour
most probable number
millimicron
nitrate
ammonium nitrogen
oxygen
phosphate
potential hydrogen, or hydrogen- ion index (negative
logarithm of the hydrogen-ion concentration)
pages
parts per billion
parts per million
pound per square foot
pound per square inch
pounds per square inch gauge
reverse osmosis
revolution per minute
raw waste load
second
Section
Standard Industrial Classification
sulfates
square
square foot
suspended solids
standard temperature and pressure
standard raw waste load
total dissolved solids
total Kjeldahl nitrogen
median tolerance limit
total organic carbon
total oxygen demand
total suspended solids
micron
microgram
volume
weight
yard
186
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TABLE XVIII
METRIC TABLE
CONVERSION TABLE
MULTIPLY [ENGLISH UNITS)
ENGLISH UNIT ABBREVIATION
acre ac
acre-feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/Pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
by
[ CONVERSION A
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555 (°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
EBREVIATI01
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
TO OBTAIN (METRIC UNITS)
METRIC UNIT
hectares
cubic meters
kilogram-calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms)
meter
*Actual conversion, not a multiplier
187
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