United States Effluent Guidelines Division EPA 440/1 ·81 /082-9 Environmental Protection WH·562 April 1981 Agency Washington DC 20460 Water and Waste Management 0 int e: • • IC rocess1n GUIDANCE DOCUMENT for the CONTROL OF WATER POLLUTION IN THE PHOTOGRAPHIC PROCESSING INDUSTRY Walter C. Barber, Jr. Acting Administrator Steven Schatzow Deputy Assistant Administrator for Water Regulations and Standards Jeffery D. Denit Acting Director, Effluent'Guidelines Division G. Edward Stigall, Chief Inorganic Chemicals and Service Industries Branch Richard Kinch John E. Newbrough Project Officers April 1981 Effluent Guidelines Division Office of Water and Waste Management U.S. Environmental Protection Agency Washington, D.C. 20460 a- CONTENTS Section Paqe I CONCLUSIONS . 1-1 I1 SUMMARY . 11-1 I11 CHARACTERISTICS OF THE INDUSTRY AND PROCESSES . 111-1 Industry Description . 111-1 Process Descriptions . I11-4 Black and White Photographic Processing . 111-4 Color Photographic Processing . 111-8 Processing Chemistry . 111-12 Processing Equipment . 111-34 In-Process Control Technologies . 111-37 Effect of In-Process Controls on Product Quality . I11-37 Silver Recovery . 111-39 Coupler Recovery . 111-46 Bleach Regeneration . 111-46 Developer Regeneration . 111-52 Water Conservation . 111-53 End-of-Pipe Treatment Technologies . 111-56 Industry Characteristics . 111-62 IV INDUSTRY CATEGORIZATION . 1v-1 Introduction . IV-1 Categorization Basis . 1v-1 Selection of Production Related Parameter . 1v-12 V PROCESS WASTE CHARACTERIZATION . v.-1 Data Base . v- 1 Processes Used . v-9 Water Use . V-17 Process Waste . v-19 Effluent Characteristics . V-25 VI SELECTION OF POLLUTANT PARAMETERS . v1-1 Description of Pollutant Parameters of Significance . v1-5 . VI I CONTROL AND TREATMENT TECHNOLOGIES ... VII-1 In-Process Control Technologies .... vii-1 End-of-Pipe Treatment Technologies . VII-23 Variability Factor .......... VII-27 VI11 COST. ENERGY. WASTE REDUCTION BENEFITS AND NON-WATER ASPECTS OF TREATMENT AND CONTROL TECHNOLOGIES .......... VIII-1 Introduction ............. VIII-1 General Cost References and Rationale .............. VIII-1 Control and Treatment Costs for Representative Photoprocessing Plants ................ VI 11-4 Non-Water Quality Aspects ....... VIII-33 IX ACKNOWLEDGMENTS ............. 1x-1 X BIBLIOGRAPHY .............. x- 1 XI GLOSSARY ................ x1-1 APPENDIX A .Telephone Contact Survey Memo .... A- 1 Y APPENDIX B .Long-Term Plant Effluent Data .... B- 1 4 FIGURES Number Paqe 111-1 Process: black and white negative - film andpaper . 111-15 I 11-2 Process: black and white reversal . 111-16 111-3 Process: color negative film, Kodak c-22 . 111-17 111-4 Process: color negative fi’lm,C-41 . 111-18 111-5 Process: color negative film, Kodak MC-42 . 111-19 111-6 Process: color negative film, ECP-1, ECN-1, ECP-2 . I 11-20 111-7 Process: color negative film, ECN-2 . 111-21 111-8 Process: color reversal film (IC), E-3 . 111-22 111-9 Process: color reversal film (IC), EM-25, E-4, ME-4, ECO-3, CRI-1 . - 111-23 111-10 Process: color reversal film (IC), E-7M . I 11-24 111-1 1 Process: color reversal film (IC), E-6 .................. 111-25 111-12 Process: color reversal film (DC), K-12 ....... e . 111-26 111-13 Process: color reversal film, (DC), K-14 . 111-27 111-14 Process: color negative paper, EP-2 . I 11-28 111-15 Process: color negative paper, EP-3, 85/86 . 111-29 111-16 Process: color negative paper, MC-111 . 111-30 111-17 ‘Process:color reversal paper, EPR-5, EPR-100 . 111-31 111-18 Process: color reversal paper, P-10 . 111-32 111-19 Process: color reversal paper, P-18 . 111-33 IV-1 Process water use vs. production . 1v-5 IV-2 Amount of silver in effluent vs. production . 1v-6 IV-3 Age of plant vs. process water use . 1v-7 IV-4 Age of plant vs. amount of silver in effluent. 1v-8 IV-5 Number of employees vs. process water use .................. 1v-9 IV-6 Number of employees vs. amount of silver in effluent . 1v-10 VII-1 Total cyanide content in effluent - no bleach regeneration . VI 1-6 VII-2 Total cyanide content in effluent - plant using bleach regeneration . VI 1-7 VII-3 Total cyanide content in effluent - bleach regeneration and ferrous sulfate precipitation . v11-8 VII-4 Silver content in effluent - no silver recovery on some fix solutions . VII-13 VII-5 Silver content in effluent - silver recovery on all waste fix . VII-14 VII-6 Silver content in effluent - waste fix not in sample . VII-15 VII-7 Effluent silver concentration vs. effluent silver amount ............. VII-19 VI 1-8 Cyanide concentra.tion vs. percent production using ferricyanide bleach . VII-20 VII-9 Process water elimination schematic ... VII-28 VII-10 Long-Term Silver Concentration in Effluent at Plant 6208 ......... VI 1-3 1 VIII-1 Silver recovery capital investment costs vs. production ............. VIII-10 VIII-2 Silver recovery operating costs vs. production ............... VIII-12 VIII-3 Reverse osmosis equipment capital invest­ ment cost vs. flow, includes reverse osmosis, conductivity control and prefilter ............... VIII-16 VIII-4 Fe EDTA bleach regeneration invested capital costs vs. production ...... VIII-18 VIII-5 Fe EDTA bleach regeneration operating costs vs. production .......... VIII-19 7 TABLES Number 111-1 Photographic Processing Establishment Categories ............... 111-2 111-2 Number of Plants and Production Breakdown by Size Category ............ 111-3 111-3 Common Color Materials ......... 111-9 III-4 Summary of Kodak "200" Plant Survey ... 111-64 111-5 Correlation of Type of Service with Production and Water Use from Telephone Survey Information ........... 111-66 111-6 Correlation of Production with Water Use from Telephone Survey Information ... 111-67 111-7 Correlation of Process Type with Production from Telephone Survey Information ... 111-68 111-8 Correlation of Processing Methods with Production from Telephone Survey Information .............. 111-69 111-9 Correlation of Replenishment Use with Production from Telephone Survey Information .............. 111-70 111-10 Correlation of Squeegee Use with Production from Telephone Survey Information ... 111-71 111-1 1 Correlation of Silver Recovery Use with Production from Telephone Survey Information .............. 111-72 111-12 Correlation of Silver Recovery Methods with Production from Telephone Survey Information .............. 111-73 111-13 Correlation of Bleach Regeneration Use with Production from Telephone Survey Information .............. 111-74 111-14 Correlation of Treatment Use with Production from Telephone Survey Information .............. 111-75 111-15 Correlation of Discharge Method with Production from Telephone Survey Information .............. 111-76 IV-1 Distinguishing Process Characteristics of Various Material Types ......... IV-3 v- 1 Production Summary ........... v- 3 v- 2 Photographic Processes Used at Plants Studied ................ v-10 v-3 Recovery and Regeneration at Plants Studied ................ V-14 v-4 Estimated Water Use for Plants in the Photoprocessing Industry ........ v-20 v-5 Processing Machine Tank Overflow Composition Without Application of In-Process Controls - Pollutant Concentration ............. V-26 V- 6 Processing Machine Tank Overflow Without Application of In-Process Controls - Pollutant Amount ............ V-27 v-7 Before and After Results of Various Silver Recovery Operations .......... V-29 v-8 Effluent Characteristics with Application of Controls - Concentration ...... V-30 v-9 Effluent Characteristics with Application of Controls - Pollutant Amounts .... v-34 v-10 Treatment Technologies Used by Photo- processors Surveyed .......... v-39 v-11 Sampling of In-Process Controls and End-of- Pipe Treatments ............ V-40 v-12 Effluent Characteristics After Application of End-of-Pipe Treatments - Polllitant Concentrations ............. v-4 1 V-13 Effluent Characteristics After Application of End-of-Pipe Treatments - Pollutant Amounts ................ V-42 VI-1 Toxic Pollutants ............ VI-2 VI-2 Conventional Pollutants ......... VI-3 VI-3 Non-Conventional Pollutants ....... VI-4 VI-4 Pollutants Found in Significant Quantities in Effluents from Photographic Processing Plants ................. VI-5 VII-1 Estimated Breakdown of In-Process Control and Treatment Use by Plant Size (Daily Production) .............. VII-2 VII-2 Total Cyanide Content in Plant Effluent of Plants Using Ferricyanide Bleach with no Regeneration .............. VII-4 VII-3 Total Cyanide Content in Effluent of Plants Using Ferricyanide Bleach Regeneration .............. VII-5 VII-4 Total Cyanide Content in Effluent of Plants Using Ferricyanide Bleach Regeneration plus FeS04 Precipitation Treatment on Waste Fix ............... VII-5 VII-5 Results of Silver Recovery on Silver Content in Plant Effluent - No Silver Recovery on Some Processes ....... VII-10 VI 1-6 Results of Silver Recovery on Silver Content in Plant Effluent - Silver Recovery on All Processes ....... VII-11 VI 1-7 Results of Silver Recovery on Silver Content in Plant Effluent - Silver Recovery on All Waste Fix But Waste Fix -Not in Sample ............. VII-12 VI 1-8 Results of Silver Recovery on Silver Content in Plant Effluent - Conventional Silver Recovery on All Waste Fix plus Additional Recovery .......... VII-16 VII-9 Effectiveness of Various Silver Recovery Procedures ............... VII-17 VII-10 Summary of Prewash Results ....... VII-21 VII-11 Effect of Countercurrent Washing and Wash Water Recycle on Effluent Hydraulic Loads ............ VII-23 VII-12 Pollutant Variability Factors .....