5-41 Five- Day Biochemical Oxygen Demand COD Chemical Oxygen Demand of Photographic Chemicals This printing replaces the 12 73 edition COD values have been added, some BOD5 values revised, new chemicals added, and discontinued chemicals deleted The infor- mation contained in this publication has been carefully prepared and IS believed to be accurate Any particular use of such information must, however, be the respon- sibility solely of the user and must be without obligation or liability on the part of Eastman Kodak Company 0 Eastman Kodak Company 1981
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5-41
Five- Day Biochemical Oxygen Demand
COD Chemical Oxygen Demand
of Photographic Chemicals
This printing replaces the 12 73 edition COD values have been added, some BOD5 values revised, new chemicals added, and discontinued chemicals deleted The infor- mation contained in this publication has been carefully prepared and IS believed to be accurate Any particular use of such information must, however, be the respon- sibility solely of the user and must be without obligation or liability on the part of Eastman Kodak Company
0 Eastman Kodak Company 1981
Table of Contents Page No
Purpose of BOD and COD Measurements . . . . . . . . . . . . . * . . . . . . .
Eastman Kodak Company has long been committed in both words and actions to the goal of a cleaner environ- ment. One small step toward this goal has been the prepa- ration of a number of publications on how the photo- graphic-processing industry can contribute toward a as well as those publications listed on page 12.
cleaner environment. These publications are components of a series known as "Information for a Cleaner Environ- ment from Kodak."
The pamphlet you are reading now is part of this series
2
r Purpose of BOD and COD Measurements
Used photographic-processing solutions are generally discharged into a municipal sewer that leads to a waste treatment plant. The regulatory agency may require pho- tographic processors and other users of the sewer to furnish a measure of the waste load that is to be dis- charged daily.
For proper operation, a treatment plant must not be overloaded. The total volume of waste and some measure of its strength is needed. The strength may be measured by the amount of oxygen that is required for the degrada- tion of the waste.
The most common measure of the waste load is the Biochemical Oxygen Demand (BOD). This test provides an estimate of the extent to which material degrades biologically during waste treatment or in a stream. Bio- chemical oxygen demand is dependent upon time and is usually measured over a five-day period. BOD is a mea- sure of the amount of oxygen required to degrade the ma- terial. lt may be expressed as a concentration in units of milligrams per litre or as a total quantity per unit of time (for example, pounds per day). Since the BOD is a static test, it does not necessarily parallel what will occur in a biological treatment system. It more closely estimates what will happen in a receiving body of water. However, it is widely used to estimate the load on a waste treatment plant and is probably as reliable as any other available test method.
Chemical Oxygen Demand (COD) is a test method that determines the amount of oxygen required to oxidize the chemicals that are measured by a particular test method. COD measures most of the photographic processing chemicals that are measured by BOD, and also measures some chemicals not measured by BOD. The COD numeri- cal value is usually larger than the BOD. However, there is no fixed correlation between the two measurements ex- cept in specific cases.
A waste effluent is described more completely by re- porting both the BOD and the COD.
As an aid to the processor, this publication lists both the BOD5 and COD values of most chemicals that can be used in the processing of Kodak photographic materials, in- cluding prepared packages of chemicals. Thus, a proces- sor may estimate the total waste load by tabulating the amounts of chemicals used and by summing the BOD5 values individually and the COD values individually,
Testing and Reliability
BOD: The BOD test is made under laboratory conditions rather than under the conditions actually prevailing in a waste treatment plant or in a stream. The dissolved-oxy- gen concentration, temperature, time, amount of sunlight, biological population, and agitation may be different. However, the method does give a fair approximation of most waste loads. The test method is described in Stan- dard Methods for tbe Examination of Water and Waste- Water, American Public Health Association. The precision of this test method, measured on a synthetic mixture in 34 laboratories with each laboratory using its own seed water, showed a standard deviation of +17 percent. The pre- cision by a single analyst was 2 5 percent.
The seed water used in our tests was taken from the
Genesee River approximately three miles below the indus- trial waste-water treatment plant operated by Eastman Kodak Company at Kodak Park in Rochester, New York. I t has been determined through tests in our laboratories that the type of seed water used in this area is not important in these analyses because all had similar microorganisms, A Weston and Stack dissolved oxygen analyzer was used to measure the dissolved oxygen content, and was cali- brated using the azide modification of the Winkler method.
In determining the BOD of a mixture of chemicals such as that found in packaged processing chemicals, the mea- surement can be made on the composite mixture, or alter- natively, on solutions of each individual chemical, and the results totaled. The latter method was chosen here to avoid interference (toxicity) by any of the other chemicals in the mixture. Certain chemicals, when present above a "thresh- old" concentration, may inhibit the action of micro- organisms, thus producing an erroneously low BODS. When these inhibiting chemicals are diluted below their "threshold" levels, as they would be in a municipal waste- treatment plant, the true BOD5 of the remaining ingredients can be measured. Nearly all effluents experience some mixing with other wastes before they are treated. When the treatment plant effluent is discharged to a stream, any residual biodegradable matter would continue to be bio- degraded.
Example: Let us assume that a photographic solution con- tains thiosulfate, sulfite, acetate, hydroquinone, and copper. (This is a hypothetical example because copper is not used in photographic-processing solutions.) The thiosulfate, sulfite, acetate, and hy- droquinone are all biodegradable and would exhibit definite measurable oxygen demands when mea- sured either as a composite soiution or indepen- dently and totaled. Copper, itself, has no oxygen demand. However, when added to the above mix- ture, it inhibits the growth of bacteria and produces an artificially low BOD5 value. When the solution passes to the drain and eventually to a treatment plant, the effect of the copper becomes negligible and the BOD5 contribution of the remaining mate- rials is the same as it would be if copper were not Dresent.
COD: This rapid test measures that portion of the waste chemicals that is oxidized by dichromate under the test conditions. Unlike the BOD test, the COD is not affected by the presence in a waste of materials that may be toxic to microorganisms. It measures oxjjgeii-demanding mate- rials such as thiosulfate, sulfite, developing agents, etc.
The basis for the method is the reaction of the test mate- rial with a boiling mixture of dichromate and sulfuric acids. A catalyst is used to provide measurement of some chemi- cals not otherwise oxidized. An additional reagent is added to avoid the interference of halides. The excess dichromate is titrated and then the calculation is made for the oxygen demand. This test method is also described in Standard Methods for the Examination of Water and Waste-Water, American Public Health Association.
The reliability of the test method, using glucose as the test chemical, is 2 8 percent (standard deviation),
3
SAMPLE CALCULATIONS FROM BODS/COD TABLES
The following sample calculations should help in estimat- ing the pounds of BOD5 or COD that might be discarded into the sewer through the discharge of photographic waste effluents.
The examples are given for BODS values. The same calculations can be applied for COD values.
A. From Prepared Solutions When BOD5 per gallon of solution is known directly from table.
If G = gallons of solution sewered P = BOD5 in pounds per gallon
and Q = pounds of BOD5 sewered Then Q = G x P
Example: I f 25 gallons of KODACHROME First Developer Replenisher, Process K-14, were discarded, what would be the amount of BOD5 sewered? Then G = 25 gallons
P = 0.1 2 pound of BOD5 per gallon (see Table VI) Q = G X P
Q = 3.0 pounds BOD5 sewered = 25 x 0.12
Example: I f 50 litres of Process EA-5 Prehardener and Replenisher were discarded, what would be the amount of BOD5 sewered? Then G = 50 + 3.8 (3.8 L/gal)
G = 13.16 gallons P = 0.21 pound of BOD5 per gallon (see Table IV) Q = G x P Q = 13.16 x 0.21 Q = 2.76 pounds of BOD5 sewered
B. From Prepared Solutions When BOD5 per pound of chemical is known directly from table.
If G = gallons of solution R = BOD5 per pound of chemical in solution S = concentration of chemical in pounds per gallon
and Q = pounds of BOD5 of chemical ThenQ = G x R x S
Remember ihai 3 m u s t be in terms of pounds per gallon. Therefore, if the amount of chemical in solution is known in grams per gallon or grams per litre or ounces per gal- lon, the following conversion factors must be used in order to convert to pounds per gallon.
Grams per gallon, multiply by0.0022 Grams per litre, multiply by 0.00834 Ounces per gallon, multiply by 0.0625
Example: I f 25 gallons of a two-component solution con- sisting of 200 grams per litre of sodium thiosulfate (penta- hydrated) and 40 grams per litre of sodium sulfite (an- hydrous) were discarded, how many pounds of BOD5 would be sent to the sewer system?
Because this solution has more than one component, the pounds of BOD5 must be determined for each compo- nent and added together to find the total of BOD5 going to the sewer.
First, for sodium thiosulfate (pentahydrated),
25 gallons 0.20 pound of BOD5 per pound of chemical (see Table I) 200 grams per litre x 0.00834 1.668 pounds per gallon G x R x S 25 x 0.20 x 1.668 8.34 pounds of BOD5 for sodium thiosulfate
Second, through a similar calculation, the Qz for sodium sulfite will be determined to be 1.001 pounds of BODS.
Because the solution is a combination of the above chemicals, the total BOD5 is obtained by adding the two results from above. Total Q, = QI + Qz
Total QT I 9.341 pounds of BOD5 sewered = 8.340 + 1.001
C. For Total Effluent from Processing Operations
The approximate BOD5 of the effluent from all of the pro- cessing operations is determined by adding the pounds of BODS from all packages and prepared solutions. That total is then divided by the number of gallons of water used by the processing operation during the time under considera- tion plus the amount of discarded solution.
Example: If, during the time that the solutions from Exam- ple A and Example B were sewered, 1000 gallons of water were used, what was the BOD5 per gallon sent to the sewer?
Q = Total BOD5
Water usage + discarded solution
= 3.0 + 9.341 = 12.341 1000 + 25 1025
interval under consideration Q = 0.01204 pound of BOD5 per gallon during
4
Table I 0 BOD5 and COD Values far Individual Chemicals
KOOAK Fixer 0.46 0.57 KODAK Fixing Bath F-5 0.50 0.64 KODAK HRP Developer 0.13 0.27 KO D AK H C- 1 10 D ev e I o p e r (Concentrate) KODAK INDUSTREX Developer Replenisher 0.37 0.61
KODAK VERSAMAT Developer Replenisher, Type A 0.08 0.13 KODAK VERSAMAT Developer Starter, Type A 1.6 2.0 KODAK VERSAMAT Fixer and Replenisher, Type A 0.55 0.70 KODAK VERSAMAT Developer Replenisher, Type B 0.17 0.25 KODAK VERSAMAT Developer Starter, Type B 1.2 1.6
KODAK VERSAMAT Liquid Developer Replenisher, Type C 0.27 0.93
KODAK VERSAMAT Liquid Developer Starter, Type C 0.88 1.1 KODAK VERSAMAT 641 Developer Replenisher 0.06 0.14
K O O A K Chemicals, Process E-4 Prehardener 0.23 0.33 Prehardener and Replenisher 0.21 0.29 Neutralizer 0.05 0.11 Neutralizer and Replenisher 0.05 0.11 First Developer ' 0.13 0.20 First Developer Replenisher 0.14 0.22
Stop Bath 0.21 0.26 Stop Bath and Replenisher 0.21 0.26 Color Developer 0.08 0.25 Color Developer Replenisher 0.09 0.26 Bleach <0.01 0.22 Bleach and Replenisher <0.01 0.23
Fixer (powder) 0.28 0.34 Fixer and Replenisher (powder) 0.18 0.23 Color Film Liquid Fixer and Replenisher
Replenisher: 0.28 0.35 Fixer: 0.17 0.21
Stabilizer 0.03 0.04 Stabilizer and Replenisher 0.03 0.04
KODAK Chemicals, Process E-6 First Developer First Developer Replenisher First Developer Starter Reversal Bath Reversal Bath and Replenisher
0.13 0.40 0.13 0.40
<0.01 <0.01 0 0.02 0 0.02
Color Developer Color Developer Replenisher Color Developer Starter Conditioner Conditioner and Replenisher
~~
Bleach BI eac h Rep1 en ish er Bleach Starter Fixer Fixer and Replenisher
0.02 0.13 0.02 0.18
<0.01 <0.01 0.02 0.06 0.02 0.06
0.08 0.96 0.08 2.0
<0.01 0.02 0.21 0.27 0.21 0.27
Stabilizer Stabilizer and Replenisher Defoamer
0.02 0.04 0.02 0.04 0 1.6
KOGAK Chemicais, Process E-GAR First Developer Replenisher Reversal Bath and Replenisher Color Developer Replenisher
0.12 0.37 <0.01 0.02
0.02 0.13
Conditioner and Replenisher 0.10 0.32 Bleach Replenisher 0.07 1.9 Fixer and Replenisher 0.21 0.27 Stabilizer and Replenisher 0.01 0.02
KODAK EA-5 Chemicals Prehardener and Replenisher 0.21 0.30 Neutralizer and Rep1 en is her 0.04 0.11 First Developer -0.11 0.22 First Developer Replenisher 0.12 0.23 Color Developer 0.10 0.28 Color Developer Replenisher 0.11 0.29
~ ~~~~ ~~
First and Second Stop Bath and Replenisher 0.22 0.27 Bleach and Replenisher 0.03 0.33 Fixer and Replenisher 0.59 0.79 Stabilizer and Replenisher (concentrate) 0.02 0.03
~ ~
KODAK Chemicals for Motion Picture EKTACHROME Films ME-4/ECO-3 Prehardener and Replenisher 0.21 0.30 ME-4/ECO-3 Neutralizer and Replenisher 0.08 0.16 ECO-3 Film-Backing Removal Solution 0 <0.01
ECO-3 First Developer ME-4/VNF-l/RVNP First Developer ECO-3 First Developer Replenisher ME-4/VNF-l/RVNP First Developer Replenisher ME-4/ ECO-3 /VNF-l / RVNP Stop Bath
ME-4/EC0-3/VNF-l/RVNP Color Developer ME-4/EC0-3/VNF-l/RVNP Color Developer
ME-4/ECO-3/VNF-l Bleach and Replenisher ME-4/ECO-3 Fixer and Replenisher
and Replenisher
Replenisher
0.08 0.13 0.08 0.13 0.10 0.16 0.10 0.16
0.23 0.28
0.11 0.28
0.11 0.29 0 0.33 0.22 0.28
~ ~~
ME-4/ECO-3/VNF-l /RVNP Stabilizer and Replenisher 0.02 0.03
Color Film Liquid Fixer and Replenisher 0.27 0.34 ME-4/EC0-3/VNF-l/RVNP Liquid Fixer
and Replenisher 0.27 0.34 ME-.I/VNF-I/RVNP Persulfate Bleach and
KODAK EKTACHROME Movie Chemicals Prehardener Starter 0 0 Prehardener Replenisher A 0.22 0.30 Prehardener Replenisher B 0.05 0.11 Neutralizer and Replenisher 0.24 0.70
First Developer Starter 40 Movie First Developer Replenisher A 40/160 Movie First Developer Replenisher B 160 Movie First Developer Replenisher A
Stop Bath and Replenisher Color Developer Starter Color Developer Replenisher A Color Developer Replenisher B
0.10 0.56 0.24 0.26 0.56 4.4 0.24 0.26
3.8 4.8 0 0 0.08 0.74 0.02 0.07
9
Table IV (continued) Pounds
KOOAK Chemical Per Gallon of
Working Solution BOD5 COD
Bleach and Replenisher 0.11 0.16 Bleach Neutralizer and Replenisher 1.8 2.4 Fixer and Replenisher 2.2 2.8 Stabilizer and Replenisher 0.22 3.4
KODAK ES-8 Chemicals First Developer 0.16 0.42 Stop Bath 0.21 0.27 Color Developer, Part A <0.01 0.10 Color Developer, Part B <0.01 0.04 Bleach-Fix, Part A 0.33 0.43 Bleach-Fix, Part B 0.06 1.6 Bleach-Fix, Part C 0.06 0.11
Fixer and Replenisher 0.56 0.76 Fixer 0.49 0.60 Stabilizer and Replenisher <0.01 <0.01
KODAK FLEXICOLOR Chemicals for Process C-41V Hardener and Replenisher 0.18 0.23 Stabilizer and Replenisher 0.02 0.03
KOOAK FLEXICOLOR AR Chemicals Developer Replenisher, Part A Developer Replenisher, Part B Developer Replenisher, Part C Bleach Starter Fixer and Replenisher Stabilizer and Replenisher
<0.01 0.02 0 0.01
<0.01 0.06 0 0 0.56 0.70 0.02 0.04
Table V BODS and COD Values for Color Paper Processing; Chemicals
KODAK EKTAPRINT 3 Chemicals Stabilizer and Replenisher 0.20 0.25
KODAK EKTAPRINT 300 Chemicals
KODAK EKTAPRINT R-5 Chemicals
Developer 0.25 0.39
First Developer Starter (concentrate) 0 0.16 First Developer Replenisher 0.08 0.20 Stop Bath and Replenisher <0.02 0.17 Stop Bath and Replenisher 0.14 0.18 Color Developer Starter (concentrate) 0.93 1.2 Color Developer Rep1 en ish er 0.26 0.40 Bleachf ix and Replenisher 0.40 0.90 Bleach-Fix Regenerator 0.40 0.90 Bleach-Fix Defoamer (concentrate) 0.96 4.0
KODAK EKTAPRINT R-100 Chemicals First Developer Starter 0 0.16 First Developer Replenisher 0.11 0.30 Stop Bath and Replenisher 0.14 0.18 Color Developer and Replenisher 0.27 0.40
Bleach-Fix and Replenisher 0.40 1.1 Bleach-Fix Regenerator 0.91 2.9 Bleach-Fix Regenerator Starter (concentrate) 0.03 0.87 Stabilizer and Replenisher 0.11 0.16
Table VI BOD5 and COD Valuesfor KODACHROME Film Processing Chemicals
KOOAK Chemical
Pounds Per Gallon of
Working Solution B O D 5 COD
KOOAK Replenishers, Process K-14 Rem-jet Removal Solution First Developer Cyan Developer Yellow Developer Magenta Develope:
Ferricyanide Bleach Fixing Bath, Formula N o . 1 Fixing Bath, Formula No. 2 Fixing Bath, Formula No. 3 Fixing Bath, Formula No. 4
RECORDAK Developer System Cleaner 0 0 RECORDAK Monobath System Cleaner 0 1.0 Stabilizer Additive <0.04 8.0
KODAK INFORMATION FOR A CLEANER ENVIRONMENT ,PUBLICATIONS NOTE: When ordering publications from Kodak, be sure to include both the title and the code number of the publica- tion. Complimentary single copies of the following Kodak pub- lications can be obtained by writing to Eastman Kodak Company, Department 41 2-L, Rochester, N.Y. 14650. Prices given are for quantities of 10. Amounts of 10 or more should be ordered from Department 454. Prices are sub- ject to change without notice. 5-8, The Kodak Silver Recovery Program The details of Kodak’s silver recovery and refining services for users of the KODAK Chemical Recovery Cartridges are described. 101’$5.40 5-9, Silver Recovery with the KODAK Chemical Recovery Cartridge, Type P The three 3 % - to 5-gallon KODAK Chemical Recovery Cartridges are described and recommended operating conditions are listed. 10/$9.00 J-gA, Silver Recovery with the KODAK Chemical Recovery Cartridge, Type 3 A description of this model cartridge intended for large scale processing operations is described in this publica- tion. 10/$5.40 5-lOA, Potential Silver Yield from KODAK Photographic Products A listing of potentially recoverable silver from various KODAK Film and Paper Products. Figures are included for both silver recovered during processing and silver from scrap film. 10/$9.00 5-IOB, Directory of Silver Services Contains the names and locations of over 200 firms throughout the United States and Canada that supply silver recovery services. No charge for copies. 5-43, A Simple Waste-Treatment System for Small Volumes of Photographic Processing Wastes Intended for photographic-processing operations that dis- charge less than 100 gallons of processing wastes per day. lO,’$5.40 5-44, In Support of Clean Water-Disposing of Effluents from Film Processing Evaluates photographic-chemical effluents in terms of sewer codes and stream standards. Methods are sug- gested for reducing the discharge of wastes. 10/$5.40 5-46, The Biological Treatment of Photographic Processing Effluents Outlines experimental work done on the biological treat- ment of photographic-processing effluents, and describes the installation and use of equipment for treating effluents biologically. Also discusses steps finishers can take to meet specifications for effluents more amenable to sec- ondary biological treatment. 10/$5.40 5-47, Chemical Composition of Photographic Processing Solutions Provides concentrations of compounds or ions in various types of processing solutions, Solution pH ranges are also given. 10/$5.40
5-48, Glossary of Terms/lndex Lists and defines chemical, photographic, and water: pollution terms as they are used in this “Information for a Cleaner Environment” literature series. Page numbers are included to the particular publications in this series in which the terms are used so that the reader can find a more extensive discussion of the terms. 10/$5.40 5-51, Silver in Photoprocessing Effluents Demonstrates that silver in photographic-processing efflu- ents is compatible with wastewater treatment and does not present a risk for receiving water. 10/$5.40 5-52, Disposal of Small Volumes of Photographic- Processing Solutions Defines “small volumes” and describes simple treatment and disposal methods for used processing solutions so that local effluent regulations are met. 10/$5.40 The following priced Kodak publications can be obtained through photo dealers, or by sending a prepaid order (in- cluding state and local taxes) to Eastman Kodak Company, Department 454, Rochester, N.Y. 14650. Prices given are for single copies and are subject to change without notice. 5-10, Recovering Silver from Photographic Materials Discusses various methods of recovering silver from waste sensitized goods and used processing solutions. List price is $4.00. 5-49, American National Standard on Photographic Processing Effluents, PH4.37-1975 Contains quantitative analytical procedures published by the American National Standards Institute. As many pro- cedures as possible are included so that this standard will be useful in a wide range of situations. List price is $2.00. 5-50, Sampling and Flow-Measurement Methods This publication will assist photolabs in knowing how to obtain proper and representative samples of effluents when asked for by local or federal agencies and testing labora- tories. List price is 52.50. 5-53, The Use of Water in Photographic Processing Discusses the theory of photographic washing, explains ways of improving the efficiency of washing, as well as other water conservation techniques. List price is $1 .OO. 5-54, Analysis, Treatment, and Disposal of Ferricyanide in Photographic Effluents-A Compendium A comprehensive collection of definitive articles on the characterization, determination, regeneration, and treat- ment of photographic processing waste effluents with par- ticular emphasis on ferricyanide bleach and ferrocyanide. List price is $5.75.
0 The following publications are available from the National Association of Photographic Manufacturers, 600 Mamaroneck Avenue, Harrison, N.Y. 10528. Single copies are free to NAPM members; nonmembers’ price is $25.00 each. Environmental Effect of Photoprocessing Chemicals, Volume I Environmental Effect of Photoprocessing Chemicals, Volume II Pathways of Photoprocessing Chemicals in Publicly Owned Treatment Works
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Consumer/ProfessionaI & Finishing Markets EASTMAN KODAK COMPANY Rochester, N.Y. 14650
2-81-F Major Revision Printed in the United States of America